Polymer Chemistry

CHM 605

CONTENTS
1. History & Basics
2. Nomenclature
3. Physical Properties
4. Molecular Weight
5. Mechanisms & Methods of
Polymerization
6.
7.

Structure & Strength of Polymers

Commercially Important Polymers

8.
9.
10.
11.

Processing of Plastics
Appendix
Laboratory Experiments
Test Questions

CHM 605
Intro to Polymer
Chemistry
Part 1
History
&
Polymer
Basics
b

Please read this excerpt from Mega Molecules by George Elias, 1987
2.1 From Rubber to Elastomers
Chance observations, purposeless toying and systematic tinkering often precede the scientific
exploration of phenomena. Such was also the case with the giant molecules, the building elements
of rubber, fibers, and plastics.
Many plants, shrubs, and trees exude when cut, a white, milk-like liquid which is called latex (from
Latin "latex"= fluid). Examples are the rubber plants in our homes and the dandelions in meadows
and lawns. Some of these lattices coagulate on exposure to air to more or less sticky, elastic masses,
but air really has not much to do with it. A rubber latex is an emulsion of microscopically small
rubber droplets (diameter ca. 0.0005-0.001mm) in a dilute aqueous solution of proteins, fats,
carbohydrates, salts, etc. The rubber droplets have a lower density than the surrounding water
solution. But being "lighter", they float to the surface similar to the cream in non-pasteurized milk
(milk is also an aqueous emulsion, albeit of protein and fat droplets). The rubber droplets then start
sticking together and form a film when the water evaporates.
Several trees of South America and East Asia are especially conspicuous with respect to this
behavior. Repeated cutting of their bark enables the gathering of more and more latex. The Maya
called such trees weeping wood (caa = wood, o-chu = weeping). The name of the trees was then
transferred by the European discoverers from the trees to the coagulated mass. The spelling was
transformed too: Caa ochu (or quechua) in Maya became cauchuc in old Spanish, and caoutchouc in
French.
The two remarkable properties of natural rubber, elasticity and stickiness, were utilized
very early. The Maya played with balls from coagulated rubber centuries before Columbus
discovered the New World. In the sixteenth century, rubber latex was used as glue to catch birds in
East Asia. At about the same time, fabrics were coated with rubber latex in Mexico give water-proof
materials. The latex could not be shipped to Europe, however, since it coagulated during the long
journey. Only in 1791, in England, did S. Peal succeed in producing rubber coated fabrics, but this
occurred only after L. A. M. Herrisant and P. I. Macquer found turpentine and ether to be solvents
for the coagulated rubber. Charles Macintosh recognized in 1826 that naphtha, a fraction of
petroleum rich in aromatics, was also suitable as a solvent for rubber. Even today, the English call
raincoats mackintoshs or macs, albeit with a wrong spelling. Fifty years earlier, in 1770, rubber
got its name after E. Nairne discovered its ability to rub away pencil marks much more effectively
than bread crumbs. What the English call a "rubber" is named "eraser" in American. Well, England
and America are known to be two nations divided by a common language. I know of an Englishman
who asked his American secretary rather innocently whether she had a rubber. Whereupon she
blushed . . .
The nice mackintoshes had a considerable disadvantage. They were sticky, especially in warm
weather. We know today that this tackiness is a direct consequence of the chemical and physical
structure of the giant rubber molecules. At that time, however, the thought prevailed that the
stickiness of natural rubber was caused by a liquid contained therein. An apparent example for
such a liquid containing, sticky material was hide glue (old carpenters glue). This glue was known
to yield a thin solution by the addition of plenty of water. Removal of water by evaporation at room
temperature or heating at elevated temperatures caused the solution to become stickier. Finally,
after all water was gone, the residue became hard and non-tacky.
A similar effect was thought to cause the stickiness of natural rubber. It was only logical to
"dry" the rubber by removing the perceived liquid. But how to do that with such a viscous ("tough"
in common parlance) material? Heating the rubber converted it into a smelly mass. One could try
to enlarge the area of rubber pieces since the rate of evaporation increases with surface area. But
cut rubber pieces always stuck stubbornly together when they were brought together into intimate
contact. Then an Englishman,

T. Hancock, had in 1819 a clever idea: if freshly cut rubber pieces always almost instantaneously
stick together, then one has to tear them apart again and again. Hancock made two rolls, each with
spikes, which rotated against each other. The rubber between the rolls was constantly torn apart
into pieces. The stickiness of the rubber did not disappear through this process, though, since we
know now that there was no liquid which could be removed. The rubber became less tough,
however, and additives could be worked in far easier. Hancock invented mastication (from Greek
mastikhan: to grind the teeth), a process still widely used by the rubber industry.
What else to do to make rubber more useful? An American Charles Goodyear, felt that a
drying agent had to be added to the rubber so that the liquid could be absorbed. Between 1831 and
1839, he systematically tried all drying agents known to him. One of the drying agents tried was
sulfur, which even today is used to "dry" wounds (it does not dry them by absorbing the water but
it kills bacteria which causes the production of pus to cease). Goodyear also tried to accelerate
drying by gentle heating. All attempts were unsuccessful until one day a mixture of rubber, sulfur
and zinc oxide were carelessly left overnight in contact with a hot oven. Low and behold: The
stickiness was gone and the previously tacky rubber was converted into a highly elastic, dry
material. Goodyear recognized the importance of his invention. But he did not find a venture
capitalist and thus kept the discovery confidential for five years. It was only 1844 that a patent
application was filed. In the meantime, Thomas Hancock got a process for the same process,
according to some sources (mainly English) because of an independent invention, according to
others (mainly American) because of reverse engineering of a Goodyear sample. Hancock also gave
the process its present name. Since heat and sulfur were used and both were attributes of the
Roman god Volcanus (Vulcan), the process was christened vulcanization.
This useful invention established the rubber industry. Rubber found more and more
applications, and its consumption jumped from 38 tons in 1825 to 388 tons in 1840 and to 8,000
tons in 1870 all collected from wild growing trees, mainly in Brazil from trees of the genera Castilla
elastic and Castilla ulai. Several Brazilian rubber barons became very rich and donated handsomely
to document their cultural devotion: They built an opera house in the middle of the Amazon jungle,
complete with imported Italian marble and Italian singer Caruso.
Brazil practically held the rubber monopoly since the very small East Asian rubber
production relied on Ficus elastica, the rubber tree of our living rooms. Englands maritime
interests generated a need of rubber for many applications and it tried therefore to break the
Brazilian monopoly. At first, the native Ficus elastica was cultivated for plantation purposes in
Englands East Asian colonies but without success: The latex stopped flowing after several cuttings.
The same experiment was repeated with the liana rubber from Africa, again without success.
Extensive investigations by J. Collins, curator of Physics Gardens of London Apothecaries Company,
showed that the genus Hevea brasiliensis would be best for plantations. Brazil held however the
monopoly for wild rubber and intended to maintain it by embargoing the export of plants and trees.
Collins tried in 1873 to smuggle out 2000 seeds but the cargo got shipwrecked. He eventually
succeeded in sending 200 seeds to England but only 12 germinated. Six of the young plants were
transferred to Calcutta where all died.
Another 70,000 seeds were brought to England by the young English coffee farmer Henry
Wickham, hiding them under banana leaves. This time 2,800 seeds germinated and 1900 plants
were grown in Ceylon. They were the base stock for all plantation rubber, first in Ceylon, then in
other East Asian countries. The first 4 tons of plantation rubber were market-ready in 1900; in the
same year, wild rubber provided 50,000 tons.
Plantation rubber is more economical and homogeneous and less soiled than wild rubber. It
has displaced wild rubber almost completely. The present day production of 3,800,000 tons of
natural rubber could not be achieved by collecting wild rubber and the repeated tapping of wild

growing trees of the genus Castilla would lead to enormous environmental damage to the Amazon
basin. However, natural rubber still provides only one third of the total world demand for
elastomers which is/now approximately 13,000,000 tons.
2.2 Cotton and Its Children
The modern fiber industry developed almost simultaneously with the rubber industry. Fibers were
used by man since prehistoric times, either as textile fibers like wool, silk, cotton, and flax, or as
hard fibers like hemp, jute, or kapok. Man uses wool the same way as nature does, as insulating
material. However, cotton finds an unnatural application as a textile fiber since it is the seed hair of
a subtropical bush, and hence does not have the same insulating function as the wool of the sheep
or our sparse body hair.
Many attempts have been made to improve cotton for human purposes, in part by tinkering
in systematic scientific investigations. Cotton was found to consist of microscopically visible cells.
Cotton, fibers were thus called les cellules by the French botanist Anselm Payen in 1838. Based
on Payens report, the French Academy of Science then named the main chemical constituent of
cotton cellulose". This name was probably created from cellule" and ose, the latter being the
usual final syllable in scientific names for sugars like sucrose or saccharose (cane or beet sugar),
lactose (milk sugar), fructose (fruit sugar), maltose (malt sugar), etc. Cellulose is chemically indeed
a sugar although it is not sweet, that property requires very small molecules since only those can
enter the molecular sized cavities of the chemical receptors of our taste buds and cause the sweet
sensation.
Cellulose is a polymerized sugar; it is a macromolecule, as we will discuss in detail later. It
is the structural component of all plants, including algae, which is a direct consequence of the giant
nature of its molecules.
Since cotton was relatively easily grown, attempts were made early to improve its textile
properties. John Mercer discovered in 1844 that cotton treated with solutions of caustic soda
(sodium hydroxide) leads to fibers with high lustre, increased strength, and improved dyeability.
Such mercerizations can also be performed with sulfuric acid.
Our modern paper is produced from wood and is a cellulose paper. Since cellulose is the
main component of both paper and cotton, it is not surprising (to us !) that L. Figuier demonstrated
to the French Academy of Science in 1846 a strengthening of paper similar to that of cotton when it
was treated with sulfuric acid. W. E. Gaine received in 1853 an English patent for the same process
which delivered a parchment-like material. This artificial parchment does not rot (in contrast to the
true parchment from animal hides) and it is also not attacked by insects either.
Six years later, another English patent of Thomas Taylor described how layers of paper
sheets can be welded together to give very resistant materials by the combined action of zinc
chloride and pressure. The process appeared to be similar to the vulcanization of natural rubber
with large amounts of sulfur to hard, black masses (Ebonite or Vulcacite), a process invented in
1851 by Nelson Goodyear, the brother of Charles. Since the rubber and the paper were both
vulcanized and the latter consisted of fibers, products from the Taylor process were called
"vulcanfiber". The material is still used today, for example, for inexpensive suitcases.
We know today that the processes leading to mercerized cotton, artificial parchment, and
vulcanized paper fiber are physical conversions of the materials; the chemical nature of the
constituent cellulose molecules is not changed. Quite different is the situation if cotton and other
cellulose containing materials are not treated by sulfuric acid alone but by a mixture of sulfuric acid
and nitric acid. This experiment was unintentionally performed in 1846 by the German Christian
Friedrich Schonbein. Chemistry professor at the University of Basle, Switzerland, Schonbein
accidentally broke a bottle with a mixture of sulfuric acid and nitric acid in the kitchen of his home
and the liquid splashed on the floor. The mixture of these two acids is so aggressive that it was

called agua regia (royal water) by the alchemists: It dissolves almost everything, even the
otherwise unassailable gold metal. Chemist Schonbein knew this of course and in order to prevent
greater harm, he took a piece of fabric to wipe it off. That fabric happened to be the cotton apron of
his wife. He rinsed it immediately with water to wash off the acid and dried it near the oven where
it promptly inflamed and burnt to ashes. Schonbein had unintentionally converted cotton into gun
cotton, i.e., he had performed a chemical transformation of cellulose into cellulose nitrate often also
called nitrocellulose. Cellulose nitrate is quite different from cellulose. It dissolves in many
organic liquids in which cellulose is insoluble. A solution in a mixture of alcohol and ether produces,
for example, a sticky liquid which can serve to cover small wounds and this collodium, the first
liquid sticking plaster, was invented.
These completely new and unexpected properties inspired other inventors. Cellulose nitrate
first led to the discovery of plastics (see below), then to the invention of man-made fibers. The first
artificial silk was made in 1879 for the threads of light bulbs by the English scientist Sir Joseph
Wilson Swan (1828 1914) who developed incandescent electric lights (yes, this was before
Thomas Alva Edison (1847 1931).
At about the same time, a Frenchman, Count Louis Marie Hilaire Bemigaud de Chardonnet
(1839 - 1924) was looking for a replacement for natural silk since the flourishing French silk
industry was threatened by the mulberry spinner pest. In 1884, he found a way to spin fibers from
cellulose nitrate solutions and to convert the flammable cellulose nitrate fibers into non-flammable
cellulose fibers. The new "Chardonnet silk" was exhibited in 1889 at the Paris World Exhibition;
two years later, the commercial production started. Many other processes and fibers followed (see
Chap. 9).
2.3 The First Plastics
Cellulose nitrate differs from cellulose not only in flammability and solubility but also in another
aspect. On gentle heating, it can be molded into hard, elastic objects, which is impossible to do with
cellulose. Films and coatings can also easily be formed from cellulose nitrate: The first movies were
recorded on cellulose nitrate films and thus also called films.
Alexander Parkes found in 1862 a method for the easy processing of cellulose nitrate after
the addition of castor oil, camphor, and dyestuffs. The products were modestly called "Parkesite;
they caused a lot of excitement and even earned a gold medal. A company was founded in 1865
with great hopes and even greater capital investment to produce "Parkesite" but technical
difficulties led to bankruptcy two years later. English and American patents of Daniel W. Spill who
used alcoholic solutions of camphor instead were equally unsuccessful.
The time was ripe for a technological breakthrough which is usually the result of the
ignorance of laymen and the hyperbole of experts. In 1869, John Wesley Hyatt was granted a patent
for the use of camphor without castor oil and without alcohol. The mixture of cellulose nitrate and
camphor could be shaped at moderate temperatures to hard objects with very smooth surface.
These were exactly the properties need for billiard balls, hitherto made from ivory, naturally
growth elephants teeth. Billiard (pool) balls of ivory often have slightly uneven surfaces and they
track erratically. Before Hyattss invention, manufacturers tried to smooth the surfaces by coating
them with cellulose nitrate, occasionally with unexpected side effects: Billiard players were literally
shooting pool since the surface coating exploded on very hard impacts, which in turn caused some
in the Wild West to draw the revolver
Hyatts invention won the $ 10,000 reward for better billiard balls, about $100,000 in
todays money. Many pool balls were however not manufactured from cellulose nitrate/ camphor,
tradenamed celluloid. This fame is claimed by a later invention, the fully synthetic Bakelite plastic,
which is manufactured from phenol and formaldehyde.

The first plastics contributed considerably to wildlife protection since far less elephants
were killed for their ivory. More than 8000 elephants died in 1864 just to cover the English
consumption of ivory. In 1909 alone, the United States imported more than 400,000 kg (880,000
lbs) of ivory which was used not only for billiard balls but also for piano keys, knife handles, and
haberdashery. This amount corresponds to 9000 elephants since a pair of elephant tusks weighs
about 45 kg (100 lbs). It is estimated that world demand for ivory required the annual killing of
100,000 elephants during the period 1860-1870.
The new plastics saved annually the lives of several tens of thousands of elephants. Even
people were protected: An estimated 4000 hunters died while hunting these large herbivorous
animals. Who thinks of plastics as protectors of the environment? Well, human desires are still at
odds with humane feelings: Elephants continue to be killed for their ivory. The latest statistics
discloses that in 1983 Germany imported 32,696 kg tusks, 580,388 carvings, and 1767 kg of other
ivory which translates into at least 2100 animals. The import of Asian ivory (but not of African
ivory carvings etc.) is illegal in the United States but what about the use of ivory in other countries
such as England, Italy and India, to name a few?
Another early plastic used casein, the white material from skim milk. A pretty horn"
(schon hom) from skim milk was already described by the German Benedictine monk Wolfgang
Seidel (14921562); the recipe is said to come from a Swiss merchant, Bartholomaus Schobinger.
The formulation was however forgotten until the American Emery Edwin Childs was granted a
patent for the production of plastic masses in 1885. In this process, whey is removed from the
curds by pressing and the remaining substance is kneaded in hot water until all fats are removed.
The mass is finally compacted in molds under the addition of dyestuffs, porcelain powder, etc. This
process is purely physical. The chemical reaction of this material with formaldehyde led, however,
in 1897 to an artificial horn which the German inventors, Wilhelm Krische and Adolf Spitteler,
called galalith", i.e., "milk stone (Greek: gala = milk, lithos = stone). Galalith is still used today for
haberdashery since it is easy to dye in beautiful colors.
Celluloid, Ebonite and Galalith are semi-synthetic products since they originate from natural
products which are then chemically converted into new compounds. The first fully synthetic plastic
was invented by the Belgian Leo H. Baekeland who lived in the United States. In 1906 he heated
various phenols with formaldehyde and produced insoluble, hard masses. The resulting phenolic
resins were resistant against solvents and heat and these Bakelites were recognized in 1909 as
excellent electrical insulators. They became one of the foundations of the modem electrical
industry.
Phenolic resins differ from cellulose nitrate especially in one property, the deformation
under heat. Cellulose nitrate can be molded at elevated temperatures to articles which retain the
shape after cooling. They can be reshaped many times on renewed heating. Materials with this
property are called themoplastics (Greek: themos=warm, plasticos=to shape, to form).
Phenolic resins, on the other hand, retain their shape upon renewed heating to the original
processing temperature; they cannot be reshaped again by heat. Plastics with this property are
called "thermosets". The difference between phenolic resins and cellulose nitrate is due to their
different chemical make-up. A short excursion into some basic chemistry is thus necessary before
we can proceed with tales of tall molecules. Those who still remember their high school chemistry
may of course skip the next chapter.

History of Natural and Synthetic Polymers

The polymer industry is a multi-billion dollar industry and yet is only about 100 years old. It is
interesting how it began ...
Natural polymeric products, e.g., pitch, milk, egg white, gum arabic, and beeswax were known to
the ancient Egyptians and Greeks. In combination with minerals, these products were used to
prepare coating compositions for walls, burial chambers, etc.
During the Chinese Chou dynasty (1169-255 B.C.) wood lacquers were developed using the sap
from the Chinese tree, Rhus Vernicifera
During the Middle Ages (500 to 1400 A.D.), linseed oil (from flax) began to be used in Europe by
painters. The monk, Theophilus, in the 11th century described the preparation (cooking) of a
varnish from linseed oil and tall oil (i.e., pine tree gum also called rosin)
Hundreds of years ago, natives of South America made use of latex, a milky white sap of
rubber trees, and coagulated it to form rubber balls that were used in the National Sport of the
Mayan Indians. In 1839, Goodyear (US) vulcanized rubber by heating it with sulfur.
Until the beginning of the 20th century, little had been done to improve on the natural materials
(polymers) available to mankind. However, the situation changed rapidly from this time forward.
After the American civil war there was a shortage of ivory (used to make billiard balls and piano
keys). A $10,000 award was offered to the first person to find an ivory replacement. In 1868,
John Hyatt, a printer, won the award by inventing the first commercial plastic, i.e., cellulose
nitrate (gun cotton). Using only natural materials, Hyatt treated cotton with HNO 3 producing
the stiff polymer. Camphor oil (a whitish, terpene ketone, C10H16O, from the camphor tree) was
added as a plasticizer making the stiff gun cotton moldable. Hyatt patented cellulose nitrate
plastic under the name celluloid which is still used today to make combs and guitar picks.
Other celluloid products, such as photographic film and plastic collars are now produced from
other polymers owing to the high flammability of celluloid.
In 1909, some 41 years later, Dr. Leo Bakeland discovered the first phenolic polymer made from
phenol and formaldehyde, called Bakelite. By molding these ingredients under heat and
pressure a hard, heat resistant plastic was formed. Phenolic resins have been used to
manufacture pot handles, electrical plug outlets and adhesives for laminating plywood.
In 1920 of Herman Staudinger (Germany) proposed his macromolecular hypothesis, saying
that substances like natural rubber were not colloidal, physical associations of small molecules
but were truly long-chain molecules of extremely high molecular weight.
It was until almost 20 years after Bakelite that the next polymers were discovered but they came as
an avalanche.
In 1927, American scientist, Wallace Carothers, synthesized and characterized alkyd resins for
paints. Carothers is considered by many as the father of polymer chemistry since his research
explained polymerization and allowed the formation of many new products.

Following is a chronology of important developments in polymer science ...

Name of Polymer

Applications

1868 Hyatt (US) celluloid

1909 phenol-formaldehyde (Bakelite)
1920 cellulose nitrate lacquers for
autos
1927 Carothers produced alkyd resins
1927 poly(vinyl chloride),
cellulose acetate plastics
1929 polysulfide (Thiokol) rubber,
urea-formaldehyde resins
1931 poly(methyl methacrylate)
plastics
Neoprene synthetic rubber
1936 poly(vinyl acetate) and
poly(vinyl butral)
1937 polystyrene (PS),
styrene-butadiene (SBR)
1938 Carothers produced nylon 66
fibers
1939 melamine-formaldehyde resins,
poly(vinylidene chloride)

1940 butyl rubber (US)

1941 low density polyethylene
WW2

silicones,
fluorocarbons,
polyurethanes,
latex paints

1947 epoxy resins and adhesives

1948 acrylonitrile-butadiene-styrene
polymer (ABS)
1949 polyester fiber
1950 acrylic fibers
1954 polyurethane foams in the US
1956 linear polyethylene
1957 polypropylene,
polycarbonates
1959 synthetic cis-polyisoprene
1960 ethylene propylene rubber
1960s cyanoacrylate adhesives,

aromatic polyamides (Kevlar),

1980's

ultra high molecular weight

polyethylene fibers (Spectra)

Manufacturer's Labeling Code:

The composition of an increasing number of plastic products is identified using the SPI
(Society for Plastics Industry) recycling code, which is usually stamped on the bottom of the
product. The number is often enclosed in the triangular arrows recycling symbol. The code
is as follows.
Examples

PETE Poly(ethylene terephthalate)

HDPE - High Density Polyethylene

V - Vinyl / Poly(vinyl chloride) (PVC)

LDPE - Low Density Polyethylene

PP Polypropylene

PS Polystyrene

Other

6
7

Poly(ethylene terephthalate), the pop bottle plastic is the most commonly recycled polymer.

You will need to learn the 7 SPI recycling symbols and names and abbreviations of
the corresponding plastics for your first and last test in this course.

Calculate the MW of PE with average DP of 100, i.e., -(CH2CH2)-100

Soln: 1mol mers = 28g, 1mol of 100mers = 28g 100 = 2800g
Calculate the MW of PE with average DP of 1000, i.e., ., -(CH2CH2)-1000
Answer: 28,000g
Calculate the MW of PE with average DP of 10,000, i.e., -(CH2CH2)-10,000
Answer: 280,000g
Calculate the DP of PE with MW = 28,000g
Solution: 28,000g/(28g/mer) = 1000mers, DP = 1000

Polymers are chain-like molecules of high molecular weight (also called macromolecules);
comprised of repeating structural units joined by covalent bonds. Polymers are built up from
smaller simpler molecules called monomers.
Poly means many and mer means part. A monomer is literally one part of the many parts in
the polymer. A different monomer, or combination of monomers, is used to make each type or
family of polymer. For example, polyethylene is made by polymerizing ethylene ...
CH2=CH2 -CH2-CH2-CH2-CH2-

or

X (CH2-CH2)n -Y

where X = an initial fragment

Y = a terminating fragment
-(CH2-CH2)n = repeating unit called a mer or mesomer
n = number or mers in the polymer, called the degree of polymerization, DP
Note that for polymers formed from symmetric monomer units such as PE, (CH2-CH2)n, or
poly(tetrafluoroethylene), (CF2-CF2)n, (Teflon), the simplest repeat units would be -CH2- and
-CF2-, respectively but by convention both methylene groups (or difluoromethylene groups)
originating from the ethylene (CH2=CH2) or tetrafluoroethylene (CF2=CF2) monomer are shown.
The degree of polymerization varies from molecule
to molecule in a sample and varies from sample to
sample. That is to say that in a given sample of
#
polymer, e.g., polyethylene, not all molecules are of
the same length and same molecular weight. The molecules
distribution of molecular weights in a given sample
generally follows a Gaussian (Normal) distribution
and the average or most common molecular weight
of the sample is reported.
The average molecular weight of polymers varies
widely, e.g., 1000 to > 1,000,000 g/mol depending
upon how polymerization took place.

Molecular Weight

(g/mol)

Homopolymers are polymers made by polymerizing

only one kind of monomer.
Copolymers are made by polymerizing > 1 type of monomer, i.e., comonomers, e.g., ethylene and
propylene comonomers can be polymerized together forming a polyethylene/polypropylene
copolymer ...
Terpolymers are copolymers comprised of 3 comonomers. Acrylonitrile-butadiene-styrene (ABS)
is a terpolymer with high impact resistance used for residential DWV piping, and auto body panels.
It is not uncommon for coatings to be formulated with 3 or 4 comonomers. This is done to modify
the properties of a coating.
Ionomers are polymers with ionic groups such as carboxylate salts. Ionomers with many ionic
groups are used as polyelectrolytes for dispersing agents and flocculants.
Oligomers are short-chain polymers ('oligo' = few) with 50 DP 3.
High Polymers are very high or ultra high molecular weight polymers, i.e., MW > 106.

Arrangement or comonomers in copolymers:

1. Random:
2. Alternating
3. Block copolymers
4. Graft copolymers

Feedstocks for Polymers:

Ethylene, C2H4, the highest volume organic chemical in North America (and the fourth
highest industrial chemical) is also the largest volume monomer for plastics.
C2H4, 37 109 lb/yr in the USA, cost ca. 25 /lb
Not only is it the monomer for polyethylene but it is the essential ingredient in
vinyl chloride (CH2=CHCl) and styrene (CH2=CH), the other two largest
monomers for plastics.
In N. America, ethane from natural gas is steam cracked at 700 C for ca. 1 s. ...
C2H6 C2H4 + H2 + other HC's
In Japan and Europe, the C5-C12 fraction (naphtha) of crude oil is cracked to
produce both C2H4 and gasoline.
Propylene and butadiene, two of the largest volume organics, are also produced
as by products
polyethylene
+ chlorine
+ benzene

ethylene

vinyl chloride
styrene

poly(vinyl chloride)

polystyrene

+ oxygen
ethylene oxide, ethylene glycol

polyethers
polyesters

polypropylene
+ ammonia
acrylonitrile

propylene

+ oxygen
+ benzene

propylene oxide
cumene, then phenol & acetone

acrylics
urethanes
phenolics

polybutadiene

butadiene

+ styrene

SBR rubber

+ chlorine
chloroprene
+ ammonia

hexamethylene diamine

neoprene
Nylon 66

Classification of Polymers Based on End Use:

1. Rubbers: In 1839, Goodyear discovered that mixing natural rubber with sulfur gave a
moldable composition that could be crosslinked (vulcanized) which produced a useful,
non tacky, stable material for waterproof raincoats, boots and tires. Even today, about
70% of all rubber ends up in tires. The pneumatic tire (Dunlop, 1888) and the use of
carbon black as a reinforcing filler and organic accelerators for sulfur cross-linking were
achieved with natural rubber.
Since WW1, most natural rubber has been cultivated in Malaysia and Indonesia.
Between WW1 and WW2 a variety of synthetic rubbers have been developed especially
in Germany and the US, e.g., Thiokol and neoprene which have high chemical resistance,
styrene-butadiene rubber (SBR) which is blended with natural rubber in tires, and
nitrile, butyl, and latex rubber.
Elastomers are rubbers which be can stretched to at least twice their original length and
return to approximately their original length when stress is relieved.
Elastoplastics are polymers with properties intermediate between plastic and rubber,
e.g. golf ball covers.
2. Plastics (also called Resins): are synthetic (i.e., non-natural) polymers which are able to
flow (i.e., can be shaped, molded, or formed) at some stage. Celluloid and Bakelite were
the first plastics. Polyethylene (plastic bags), polystyrene (weigh boats) and poly(vinyl
chloride) (shower curtains) are among the largest volume plastics. Additives include
fillers, colorants, reinforcing agents, UV inhibitors, flame retardants, etc.
3. Fibers: are long strands of polymers (natural or synthetic) which are woven into fabrics,
rope, and cordage. Important fibers for the garment industry include wool, cotton,
nylon, polyesters. Polypropylene fibers are produced in large volumes for rope,
furniture and carpet manufacture.
4. Coatings : include paints, varnishes, and deposited films. Examples include latex, acrylic,
alkyd, oils, lacquers, epoxies, etc.
5. Adhesives and Sealants : are similar to coatings but differ in that they are used to bond
two different surfaces. Important examples of adhesives include cellulose acetate
(paper glue), epoxies, and cyanoacrylate (Crazy glue). Sealants include poly(dimethyl
siloxane), silicone.
6. Films : are thin polymeric sheets such as those used in fabricating polyethylene bags and
vapor barriers, poly(vinylidene chloride) sheets (Saran wrap), etc.
7. Composites : combine resins and fillers as in fiberglass reinforced plastics (FRP), or
polymer films and polyaramid (Kevlar) or Spectra fibers (used in bullet proof vests).
Light weight, high strength materials are usually composites. Kevlar and Spectra
polymers boast 10 times the strength of steel on a weight basis. Other uses include
aerospace products, e.g., helicopter fuselages.
8. Cellular Materials: include rigid and flexible foams, e.g., polyurethane foams in
upholstery and polystyrene foams in packaging materials and insulating materials.
9. Biopolymers: are naturally occurring macromolecules produced by plants and animals,
e.g., fibrous proteins such as keratin (hair, horn, feathers, fingernails), globular proteins
[casein (milk), albumin (eggs), zein (corn)], polyamino acids, enzymes, etc.
7

Classification of Polymers Based on Structure:

Polymer chains are linear, branched or cross-linked ...
1. Linear:
2. Branched:

3. Crosslinked (or Network):

Functionality:
Carothers defined functionality as the number of bonds a monomer can form. All
monomers must be able to form at least 2 bonds per molecule, i.e., have a functionality of at
least 2, otherwise the molecules could not polymerize.
Ethylene, CH2=CH2, with 1 double bond can bond to 2 other molecules so it has a
functionality of 2. This is true for most vinyl compounds, i.e., vinyl chloride, styrene
(vinyl benzene), etc.
Butadiene, CH2=CH-CH=CH2, with 2 double bonds can bond to 4 other molecules so it
has a functionality of 4.
Ethylene glycol, HOCH2CH2OH, with 2 hydroxy groups, has a functionality of 2
What is the functionality of propanetriol, HOCH2CH(OH)CH2OH ?
Linear polymers (and some branched) are formed by monomers with a functionality of 2.
Network polymers (and some branched) require monomers with a functionality of at least
3.

Classification of Polymers as Thermoplastic or Thermoset:

Linear and branched chain polymers are thermoplastic, e.g., polyethylene, polystyrene, PVC.
Thermoplastics exhibit the following properties ...
1. they are linear or branched
2. soluble in appropriate solvents
3. fusible, i.e., melt when heated
4. waste materials can be recycled (10-20 ), but they gradually degrade after repeated cycling
Thermosets such as epoxies, rubber, phenolics, exhibit the following properties ...
1. they are crosslinked (or network) polymers
2. insoluble in solvents - dont dissolve but may swell
3. infusible - cannot be melted (heat resistant) but will decompose at high enough
temperature
4. once polymerized, they cannot be reprocessed (or only with difficulty, e.g., tires, foams)

Note that only thermoplastics can exhibit plastic flow and solubility because they are composed of
large but singular (unconnected) molecules. Thermosets are composed of an infinite network of
bonded molecules which cannot be separated without breaking covalent bonds. Rubber is a good
example.
Natural rubber consists mostly of a linear polymer that can be crosslinked to a loose network by
reaction with 1 to 3% sulfur. The same polymer reacted with 40-50% sulfur is 'hard rubber', a
tight network polymer, used for pocket combs and bowling balls. We are accustomed to
thinking of molecules as submicroscopic; however the major portion of polymer in a tire or
bowling ball is really one molecule. This is because all the separate molecules in the tire were
connected to one another by sulfur cross-links during 'vulcanization'.
Calculate the molecular weight of a 10 pound bowling ball polymer. (ans. = 2.7 1027 g/mol)

Classification of Polymers by Chemical Makeup:

Polymer strengths are determined not only by the main chain covalent bond strengths (50-150
kcal/mol) but also by secondary intermolecular or van der Waals' forces (2-10 kcal/mol).
In general, covalent bond strength governs photochemical and thermal stability
(decomposition). For example, sulfur-vulcanized rubber is more likely to degrade at the
comparatively weak -S-S- bonds (51 kcal/mol) than at the strong -C-C- bonds (83 kcal/mol).
On the other hand, secondary forces determine most of the physical properties we associate
with specific compounds. Melting, dissolving, vaporizing, adsorption, deformation, and flow
involve the making and breaking of intermolecular 'bonds' so that molecules can move past one
another or away from each other.
Polymers with polar functional groups, particularly with H-bonding (-HO-, -HN-, -HF-,)
have strong intermolecular forces and have relatively high softening temperatures, e.g.,
PE (nonpolar HC) = ~110 C
Nylon 66 (polar, polyamide) = ~ 200 C
Cotton (cellulose) is a linear polymer but its high density of strong H-bonds gives it
properties normally associated with crosslinked polymers, i.e., insolubility and infusibility.
Kevlar (a tightly packed, polar, polyaramid) = ~500 C

Overview of Forces Associated with Bonding (Intramolecular and Intermolecular):

Intramolecular Forces (Forces within chemical units hold atoms/ions together in molecules.)
Force

Model

Ionic

Covalent
+

Metallic

+
+

Cause

Energy
(kcal/mo
l)

Example

cation to anion

100-1000

Na+Cl-

nuclei to shared
e- pair

35-250

H-H

cations to
delocalized e-'s

18-240

Fe

Intermolecular Forces: (Forces between chemical species.)

Ion-dipole
d-

d+

dipole-dipole
d-

H-bond

dA

Ioninduced dipole
Dipoleinduced dipole
Dispersion
(London Forces)

d+

d-

d+

d-

d+
H

d:B

ion charge to
dipole charge

10 - 140

dipole charges

1-6

.. H
O
..
H

Na+

d+

(F, O, or N
bond to H) to
(F, N, or O)

2.5 - 10

ion charge to
polarizable ecloud

0.7 - 4

dipole charge
to polarizable
e- cloud

0.5 - 2.5

polarizable eclouds

0.01 1

Cl

.. H
O
..
H

Fe+3

Cl

Ne

Cl

.. H
O
..
H

Br2

Cl

Cl

Ne

London Forces, the weakest of all intermolecular forces, can become large (up to 10 Kcal/mol) in very large
molecules such as high molecular weight polymers, e.g., high molecular weight polyethylene.

10

Classification of Polymers by Chemical Makeup

The forces that hold polymers together can be divided into two kinds; intermolecular and
intramolecular forces
Intramolecular forces (covalent bonds) hold the mesomers together in a polymer chain.
bond strength

mesomer

bond

-(CH2-CH2)-

Csp3 ----Csp3

376

90

-(CH=CH)-

Csp2 Csp2

611

146

S crosslinks

S-S

213

51

kJ/mol

kcal/mol

Intermolecular forces (secondary forces) result in attraction between different polymer

chains.
For polymers, secondary forces include:
1. induced dipole induced dipole forces (London Dispersion forces) in non polar
polymers (e.g., PE, PS, PP)

2. dipole-induced dipole & dipole-dipole forces in polar polymers

(e.g., PVC, cellulose, etc.)
cellulose, a 1,4'-O-(b-D-glycopyranoside) polymer
CH2OH
4'

Cl

Cl

Cl

Cl

CH2OH

..
O
..

Cl

Cl

Cl

OH
OH

OH

Cl

..
O
..

OH

b-D-glucopyranoses
1,4'-b-glycosides

11

3. ion-dipole & ion- induced dipole in ionomers (e.g., poly(vinyl acetate) Elymers
glue)

C O

C O

O-

O-

O-

C O

C O

O-

O-

O-

In network polymers, crosslinked chains are held together by both intermolecular and
intramolecular forces. Sulfur is often used to crosslink unsaturated thermoplastic
polymers.
CH3

CH3

CH3

S6

S6

isoprene
(latex from rubber tree)

CH3

CH3

CH3

CH3
1,4-polyisoprene
(natural rubber)
with sulfur crosslinks

Describe the type of intramolecular and intermolecular forces in polyamides like Nylon

N
O

H
N

12

Classification by Physical State:

Polymers may be partially crystalline or completely disordered (amorphous). The
disordered state may be glassy and brittle or it may be molten and viscous or it may be
rubbery.
In general, branched and crosslinked polymers tend to be amorphous while a linear
polymer can be either amorphous or partly crystalline depending upon how it is
manufactured. Branching interferes with the orderly packing of molecules, so that
crystallinity decreases.
If the polymer chain contains carbon atoms with two different substituents, the carbon is
asymmetric, since the two parts of the chain with which it is connected are different also.
Such asymmetric carbons can exist in two different spatial configurations which are not
interchangeable in stereoisomers without breaking covalent bonds. Vinyl polymers are
formed in any of three different configurations or 'tacticity'.
Consider the linear polymer, polypropylene.
CH3

CH3
CH2

CH

propylene

( CH2

C)
n

H
polypropylene

In the repeating unit, (the mer), every other carbon is asymmetric. Three tacticities of PP
can result. These are best visualized by looking at the polymer in its planar zigzag
conformation.
isotactic PP has each pendant methyl group on the same side of the chain, that is all d or
all l, using the terminology of stereochemistry. The regularity of this arrangement
allows orderly packing necessary for high crystallinity. Isotactic polymers form helices
to alleviate steric strain.

syndiotactic PP has a regular alternation of pendant groups. This arrangement can also
produce high crystallinity and the planar zigzag conformation is sterically unhindered.

13

Random placement of methyl groups gives PP an atactic structure which cannot allow a
highly crystalline packing arrangement.

Until the advent of coordination complex catalysts, it was difficult to produce synthetically
any structure except atactic. Increasing the crystallinity of a polymer often improves its
physical properties, i.e., m.p., tensile strength, etc. So it is desirable to be able to control the
stereochemistry and hence the crystallinity during polymerization.
A second type of stereoisomerism in polymers is the cis-trans variety. Again, with the aid of
special catalysts, monomers like 1,3-butadiene can be polymerized to either the cis or trans
polymers (cis- or trans-1,4-polybutadiene in this example) ...
CH2=CH-CH=CH2
1,3-butadiene

( CH2-CH=CH-CH2 )
1,4-polybutadiene

Trans-1,4-polybutadiene, when vulcanized, produces a stiff inferior rubber.

Cis-1,4-polybutadiene produces a superior, flexible rubber

14

CHM 605
Part 2
POLYMER
NOMENCLATURE

15

Nomenclature of Polymers:
As in the case of organic chemistry in general, the nomenclature of polymers is not fully
systematic and the actual nomenclature is a mixture of common and IUPAC names. The
three methods of naming polymers are ...
1. Common names based on the monomer: Add 'poly' as a prefix to the monomer name.
For example, ethylene polymerizes to polyethylene.
For complex monomers,
parentheses are also added, e.g., vinyl chloride polymerizes to poly(vinyl chloride)
2. Trade names and acronyms:
memorized.

These are historical and industrial and must be

3. Nomenclature based on the IUPAC system: The simplest repeat unit in the polymer,
sometimes called the constitutional repeat unit, CRU, is named and then prefixed with
'poly'. For example, (CH2-CH2)n is named polymethylene since the simplest repeat unit
is
actually
-CH2-. Similarly, (CF2-CF2)n is named poly(difluoromethylene).

Monomer
CF2=CF2
tetrafluoroethylene

Polymer
(-CF2-CF2-)n
Trade Name (Dupont)
Teflon
Common name
poly(tetrafluoroethylene)
IUPAC name
poly(difluoromethylene)

In order to write a common name for a polymer, one must know the name of the
monomer.

16

Name the following polymers. c = common, I = IUPAC.

)n

(
Cl

c:

poly(vinyl chloride)

I:

poly(chloroethylene)

)n

O)

OH

c:
I:

F F

F F

c:
I:

Cl

Cl

Cl

Cl

Cl

Cl

c:
I:
17

O
O

c
I

c
I

O
O

c
I

N
H

18

Complete the following tables and learn these important polymers:

Monomer Structure

CH2=CH2
CH2=CH(CH3)

Monomer Name
ethylene
propylene

Polymer Repeating Unit

CH2 CH2

Common Name (Abbrev.), Trade name

polyethylene (PE), (LDPE), (HDPE)
polypropylene, (PP)
Herculon upholstery,

vinyl chloride

poly(vinyl chloride), (PVC)

Vinyl, Tygon tubing

vinylidene chloride

poly(vinylidene chloride)
Saran wrap

tetrafluorethylene

poly(tetrafluoroethylene), (PTFE)
Teflon

styrene

polystyrene, (PS)
Styrofoam

vinyl acetate

poly(vinyl acetate), (PVA), (PVAc)

Elymers Glue
poly(vinyl alcohol), (PVAL)

Monomer Structure

Monomer Name
acrylonitrile

Polymer Repeating Unit

Common Name (Abbrev.), Trade name

polyacrylonitrile, (PAN)
Orlon fibre

acrylic acid

poly(acrylic acid)

methyl methacrylate

poly(methyl methacrylate), (PMMA)

Plexiglas, Lucite, Perspex

1,3-butadiene

trans-1,4-poly(1,3-butadiene)

1,3-butadiene

cis-1,4-poly(1,3-butadiene)

2-chloro-1,3butadiene

polychloroprene,

(chloroprene)
2-methyl-1,3butadiene

Neoprene
polyisoprene,

(isoprene)

cis-1,4-polyisosprene = latex rubber and

trans-1,4-polyisoprene = Gutta Percha

ethylene oxide

poly(ethylene oxide) = poly(oxy-ethylene)

Carbowax

formaldehyde

polyformaldehyde,
Delrin

20

CHM 605
Part 3
PHYSICAL
PROPERTIES
OF
POLYMERS

Physical States and Transitions:

Consider a long, regular polymer chain connected by a series of single bonds, e.g. PE or
polystyrene (PS). With the potential for free rotation around single bonds, the chain might
assume an infinite number of conformations in space, however, during these rotations, the
bond angles and distances remain fixed. Three extreme conditions of physical state are
possible ...
1. Completely free rotation in a liquid state:. When a polymer, i.e., a thermoplastic is heated
above its melting temperature, its continuously wriggling molecules can slip past each
other. The higher the temperature, the more intense the molecular motion. This liquid
state is a 'melt'.
2. No rotation in a tangled solid state. On cooling a polymer from the melt, at some
sufficiently low temperature, the polymer will not have sufficient kinetic energy to
overcome the energy barriers (steric hindrance or polar attraction) for rotation around
single bonds to occur. If the cooling was rapid, molecules do not have time to arrange
themselves in an ordered (crystalline) manner and are trapped in a disordered, chaotic,
entangled state. It is amorphous.
3. No rotation in an orderly solid state. If cooled slowly from the melt (or stretched while
cooling) the chains of polymer may align themselves into a regular crystallatice. This is the
'crystalline' state.
Each of these is a simplification. Other factors modify the physical state of a polymer, e.g.,
1. the presence of double bonds in the chain do not permit free rotation
2. thermoset (crosslinked) polymers inhibit rotation
3. longer chains experience greater intermolecular attraction and entanglement per
molecule than shorter chains of the same polymer, i.e., MW is a variable
4. branching interferes with orderly packing
5. the presence of large bulky groups inhibit rotation, e.g., PS is largely amorphous
6. the presence of highly polar groups resist free rotation
7. the presence of solvents allow rotation below the normal solidification temperature
As a result, polymers may be completely amorphous, partly crystalline, or wholly crystalline.

Amorphous polymers tend to be transparent, e.g., amorphous poly(ethylene

terephthalate), (PET), for pop bottles and poly(vinylidene chloride) for Saran Wrap.

Crystalline polymers are opaque; their crystals scatter light, e.g. 95% crystalline High
Density Polyethylene (HDPE).

Partly crystalline polymers contain crystalline domains (crystallites) mixed with

amorphous domains, e.g., 55% crystalline Low Density Polyethylene, (LDPE), for
plastic bags is translucent.

Illustration of a Partly Crystalline Polymer

The Glass Transition Temperature (Tg):

Non polymeric materials have only one phase change between the solid and liquid states. This
occurs at the melting point (also called the freezing point). For example, sodium chloride
melts (freezes) sharply at 801C and water melts (freezes) at 0C.
Many polymeric materials have two phase changes between the solid and liquid states. For
example, low density polyethylene (LDPE), is a liquid above 100C (the melting point, Tm).
When cooled below Tm , it is a flexible (leathery) solid. However, on further cooling, the
flexible solid becomes a stiff, brittle solid (a glass) at -110C. The temperature at which the
transition from a flexible (leathery) solid to a stiff, brittle solid (glass) is called the stiffening
temperature or the glass transition temperture (Tg).
Tm, sometimes called the first-order transition temperature, is often actually a temp.
range.
Tg, sometimes called the second-order transition temperature, defines a boundary
between the rubbery or plastic state and the brittle, glass state. Many polymers show an
abrupt change in physical properties at this point, i.e., density, specific heat, and refractive
index as well as flexibility, elasticity, and dielectric properties.
The following figure shows the changes in specific volume with temperature for an amorphous
polymer not having a true melting point, as well as for a crystalline polymer.
Tg is assumed to be the same for both polymers.
Note the abrupt change in density at Tg as
segmental motion stops.
By rapidly cooling a crystalline polymer specifi
amorphous
from the melt, it may follow the upper c
volum
crystalline
(amorphous)
curve
since
rapid e
solidification may not allow time needed (mL/g)
for orderly packing but may freeze the
molecules in the tangled, melt-like
arrangement.

Completely crystalline polymers

have a Tm but no Tg. They change
sharply from a liquid to a brittle
Tg
solid at Tm (similar to NaCl & H2O).
Tm

Completely amorphous polymers

have a Tg but no Tm. When heated, they gradually soften and liquefy over a
temperature range (similar to glass).

Partly crystalline (partly amorphous) polymers have both a Tm and a Tg.

Plasticizers:
Plasticizers are nonvolatile solvents purposely added to lower the stiffness (Tg) of a polymer. The
plasticizer occupies space between molecular chains and reduces intermolecular attraction acting
as a lubricant. For example, polyvinyl chloride, a stiff polymer with a high Tg (82C) is made
flexible by the addition of up to 40% dioctylphthalate or tricresylphosphate plasticizer. Tg drops
to ca. -80 C. The result is a flexible plastic used for raincoats and shower curtains. Fogging or
sweating may occur at high temperatures, i.e., migration of the plasticizer occurs eventually
resulting in the onset of embrittlement.
Many commercial fibers are plasticized by small amounts of water. The familiar process of steam
ironing a garment usually takes place between Tg and Tm. The moisture lowers Tg below the iron
temperature allowing the removal of creases (due to polymer flow). The garments shape is locked in
place when the heat and moisture are removed leaving a wrinkle free appearance.
Values of Tg for some common plastics are listed. Study these and be able to explain the relative
differences.
Polymer

Tm (C)

Tg (C)

polyethylene (high density-high MW)

137

-20

polyethylene (low density-low MW)

100

-110

polypropylene (isotactic) high

density

ca. 160

30

polypropylene (atactic) low density

ca. 130

-20

polystyrene

160

100

poly(methyl methacrylate)

160

105

poly(vinyl chloride)

212

82

polyacrylonitrile

267

45

poly(ethylene terephthalate)

267

80

Nylon 6,6 (a polyamide)

267

45

Non polar polymers have

low melting points.
The same polymer, loosely
packed has lower Tg than
when tightly packed.

Bulky side chains increase

Tg as in PS vs. PE & PP.

Polarity incrases Tm and

Tg values.

Structure and Properties Conventional Polyethylenes:

As a result of different polymerization processes for commercial PE and the versatility of these
processes, a number of types of PE are manufactured, each specially engineered for particular
applications. Table II compares some of the fundamental properties of the more important
commercial PE's. Amorphous PE and highly crystalline polymethylene are also included to
delineate the full range of properties attainable with PE.
Table II. Physical properties of polyethylenes related to molecular structure.
Type
of

Crystallinit
y

Density
g/cm3

Melting
Point
C

Tensile

# Branches

Strength

per 1,000

MPa

C atoms

PE

Amorphous

0.85

LDPE

50-70

0.91-0.925

106-112

9-15

20-40

LLDPE

65-80

0.92-0.94

125

13-20

10-25

HDPE

80-95

0.9410.965

125-138

21-37

< 5-10

Polymethylene

> 95

0.97

143

unbranche
d

The tabled data reveals clear trends which can be understood in terms of the molecular
structure of these polymers. The structural variables are twofold: (1)...the length and
frequency of occurrence of chain branching, (2)...the average molecular weight and molecular
weight distribution. In the case of polyethylenes, the stereochemistry of the polymer is not a
variable because of the symmetry of the ethylene monomer.

Crystallinity:
The extent to which polymer molecules will crystallize depends on their structures and on the
magnitudes of the secondary bond forces (van der Waals' forces) among the polymer chains.
The greater the linearity of the polymer molecule, the greater the tendency toward
crystallization.

Linear PE has essentially the best structure for chain packing. Its molecular structure is
very simple and perfectly regular, and the small methylene groups fit easily into a crystal
lattice. Linear high density PE, with infrequent branching, therefore crystallizes easily and
to a high degree (over 90%) even though its secondary forces are small.

Branching impairs the regularity of the structure and makes chain packing difficult.
Branched low density PE, with frequent branching, is thus only partially (50-70%)
crystalline. Many of the differences in physical properties between low-density and highdensity PE's can be attributed to the higher crystallinity of the latter.

Thus, linear PE has higher density than the branched material (density range of 0.94-0.965
g/cm3 vs. 0.91-0.94 g/cm3), higher melting point (typically >125 C vs. 112 C), greater
stiffness and tensile strength, greater hardness, and less permeability to gases and vapors.

CHM 605
Part 4
MOLECULAR
WEIGHT
OF
POLYMERS

Molecular Weight:
Because of their large molecular size, polymers possess unique chemical and physical
properties. These properties begin to appear when the polymer chain is of sufficient length,
i.e., when the molecular weight exceeds a threshold value, and becomes more prominent as
the size of the molecule increases.

Note the increase in melting points with increasing molecular weight in the paraffin series:
C20H42 (35 C), C30H62 (65 C), C40H82 (81 C), C50H102 (92 C), C60H122 (99 C), and
C70H142 (105 C). Highly linear polyethylene of molecular weight greater than three
million exhibits a melting point of 132 C. The melting point of 100% crystalline,
completely unbranched polyethylenes of infinitely high molecular weight (density at 25 C
of 1.002 g/cm3) is reported as 143 C.
The dependence of the melting point of polyethylene on the degree of polymerization (DP)
is shown in Figure 2.
140
120
100
80

mp
( C)

60
40
20
0
0

500

1000

1500

DP of PE

Figure 2. Melting point of PE versus degree of polymerization.

The dimer of ethylene (butylene) is a gas, but oligomers with a DP of 3 or more (that is, C6
or higher paraffins) are liquids, with the liquid viscosity increasing with the chain length.
Polyethylenes with DP of about 30 are grease-like, and those with DP around 50 are
waxes.

As the DP value exceeds 400, or the molecular weight exceeds about 10,000, polyethylenes
become hard resins with melting points above 100 C. The increase in melting point with
chain length in the higher molecular weight range is small. Here crystallinity has a greater
influence on the melting point.

Figure 3: Variation of Physical Properties with Molecular Weight

commerci al range
of PE 's

P
r
o
p
e
r
t
y

tensi l e strength
i mpact strength
mel t vi scosi ty

Mol ecul ar W ei ght

Variation in molecular weight will also lead to differences in mechanical properties, i.e., the
higher the molecular weight the greater the number of points of attraction and entanglement
between molecules. Increased molecular entanglement hinders crystalline packing and
thereby lowers density.

Molecular weight also influences properties related to large solid deformations, i.e., tensile
strength, impact strength, elongation at break, and melt viscosity; all of these increasing
with higher molecular weight. Note in Figure 3 that the strength properties increase
rapidly at first as the chain length increases and then level off, but the melt viscosity
continues to increase rapidly.
Polymers with very high molecular weights have superior mechanical properties but are
difficult to process and fabricate due to their high melt viscosities. The range of molecular
weights chosen for commercial polymers represents a compromise between maximum
properties and processability.

Molecular Weight Distribution of Polymers:

In ordinary chemical compounds such as sucrose, all molecules are the same size and
therefore have identical molecular weights (M). Such compounds are said to be monodisperse.
In contrast, virtually all synthetic polymers and some natural polymers are polydisperse. Thus
most polymers do not contain molecules of the same size and therefore do not have a single
molecular weight.

The extent of variation of molecular weight and size in a polymer sample is known as its
molecular weight distribution, (MWD) and the MWD has considerable influence upon the
physical properties of the polymer.
The molecular weight of a polymer is reported as an average. Since it is not generally possible
to physically segregate, count and weigh all the molecules of a sample, average molecular
weight is determined by a variety of techniques, each giving slightly differing values.

Methods of determining molecular weight include the following

1. end group analysis, e.g., titration of reactive end groups such as carboxylic acid
groups or amine groups
2. colligative properties, i.e., vapor pressure lowering, boiling point elevation, freezing
point depression, and osmotic pressure. Recall that each of these effects are
proportional to the number of moles of solute (polymer) present in a solvent.
3. light scattering: The intensity of light scattered is proportional to the square of the
mass of the particle in solution
4. ultracentrifuge: After centrifuging a solution of the polymer at high speeds for
several weeks, a concentration gradient is established with larger particles in the
lower layers of the solution. The concentration of polymer at various depths is then
determined by optical methods.
5. viscosity: Ostwalt viscometers are used to measure relative viscosity of dilute solutions
of polymers. The viscosity is directly proportional to the polymer chain length.
6. gel permeation chromatography: (size exclusion chromatography). A crosslinked
porous polystyrene packing ('gel') separates polymer molecules based on their size.
The flow of smaller polymer molecules is slowed down as they diffuse into the pores
of the gel while larger molecules move through the column more quickly. A suitable
detector (e.g. photometer, conductance, etc.) indicates the relative concentrations.

Molecular Weight Determination of Polymers

A non polymeric substance has a fixed molecular weight. For example, all glucose molecules
(C6H12O6) have the same molecular weight (180.15 g/mol).
A sample of a polymer contains chains of different lengths. Thus a polymer does not have an
exact and absolute molecular weight. If we could separate all polymer chains in a sample and
count the number of chains of each weight, we could then calculate an average molecular
weight for a given sample. This is physically impossible to do.
In order to determine the average MW of a polymer sample we conduct chemical and/or
physical tests. Different tests may give different values for the molecular weight of the same
sample. The tests may be grouped into three types; number average MW tests, weight average
MW tests and viscosity average MW tests.
Number Average MW Tests:
These tests measure the number of molecules present in a sample.
1. End Group Analysis involves titrating reactive end groups with a standard acid or base
titrant. This only works for polymers that have reactive end groups. For example,
polyesters (made by reacting a diol with excess diacid) will have carboxylic acid end
groups on all chains. Titration of a weighed portion of the polymer with standard
NaOH yields the number average MW of the polymer. Similarly, a polyamide made by
reacting a diacyl chloride with excess diamine produces a polymer with amine end
groups on all chains. They can be titrated with standard HCl titrant.
Calculate the number average MW of a polyester given that titration of a 10.00 g
sample requires 50.00 mL of 0.0100 M NaOH titrant. (ans. 40,000 g/mol)
3 roses cost $4
9 roses cost $x =

2 tires cost $90

$4 x (

9 roses
) $12
3 roses

4 tires cost $x =

$90 x (

4 tires
) $180
2 tires

2. Colligative Properties include vapor pressure lowering, boiling point elevation,

freezing point depression and osmotic pressure. These properties vary in proportion
to the number of moles (mole fraction) of a substance and hold for both polymeric and
non polymeric substances.
a) Vapor Pressure Lowering: Recall from Raoults law that the vapor pressure above a
solution is inversely proportional to the mole fraction of non volatile solute dissolved
in a solution.
Psoln = (P0solvent)(xsolvent) where P = vapor pressure and x = mole fraction
A solution of the polymer can be boiled at room temperature by evacuating the vapor
space above the solution. Since a liquid boils when its vapor pressure equals the
pressure of atmosphere above it, the polymer solution will boil when the applied
pressure becomes equal to the vapor pressure of the solution. By accurately
measuring this pressure and the pressure at which pure solvent boils (at the same
temperature), the number average MW can be calculated.
Calculate the number average MW of a water soluble polymer given the following
data.
10.000g polymer are dissolved in 36.03 g H2O. At 20C this solution boils at 17.46
mmHg. At the same temperature, pure H2O boils at 17.53 mmHg. (ans. = 1247 g/mol)

b) Boiling Point Elevation: The boiling point of a liquid is elevated if a non volatile solute
is dissolved in it (because its vapor pressure is lowered as explained above).
Tb = kbm

where Tb = bpelevation, m = molality of solute, kb is constant for a solvent

Calculate the number average MW of a polymer given that when 10.000g polymer are
dissolved in 100.00 g CCl4, the solution boils at 76.84 C. The normal bp of CCl4 is 76.74
C. The molal bp elevation constant for CCl4 is 4.95 Kelvinskgsolventmolesolute-1.
(ans. = 4950 g/mol)

Boiling Point Elevation of Calcium Chloride Solutions

Freezing Point Depression of Calcium Chloride Solutions

c) Freezing Point Depression: The freezing point of a liquid is depressed when a non
volatile solute is dissolved in it. (Recall that NaCl and/or CaCl2 are applied to roads to
melt ice, by lowering the freezing point of water).
Tf = kfm

where Tf = fpdepression, m = molality of solute, kf is constant for a solvent

Calculate the number average MW of water soluble polymer given that the freezing
point of an aqueous solution of the polymer is 0.14 C. The solution is prepared by
dissolving 72.00 g polymer in 500.00 g H2O. The molal fp depression constant for water
is 1.86 Kelvinskgsolventmolesolute-1. (ans. = 1910 g/mol)

d) Osmotic Pressure: Osmotic pressure is that pressure, which must be applied to a

solution to prevent osmosis, i.e., to prevent the passage of pure solvent through a semi
permeable membrane into a solution.
= MRT

where = osmotic pressure. M = molarity, R = gas constant, T = Kelvins.

Unlike the other colligative properties, osmotic pressure displays a large response for
even dilute solutions. For example, calculate the osmotic pressure (atm and m H2O) of a
solution of 6.00 g urea (MW = 60.0 g/mol) dissolved in 2.00 L H2O at 20C. The gas
constant (R) is 0.08206 Latmmol-1K-1. (ans. = 1.20 atm and 12.4 m H2O!)
Calculate the number average MW of a water soluble polymer given that when 15.00 g
polymer is dissolved and diluted to 200.00 mL, its osmotic pressure at 20C measures
0.00605 atm (ans. = 298,000 g/mol)

Weight Average Molecular Weight Tests:

These tests measure the average size of polymer molecules. Size is proportional to weight.

Intensity

1. Light Scattering: Solutions of non polymeric

solutes, like aqueous NaCl, are transparent to light
because the solute and solvent molecules are much
smaller than the wavelength of light. The light
bends around small molecules and ions and such
particles are therefore invisible. Polymer
molecules, however, are larger than the wavelength
of UV and, in some cases, visible light.
When light passes through a solution of polymeric
solutes, the light is scattered. The intensity of light
scattered is proportional to the square of the mass
of the particle in solution.

weight avg. MW

To use light scattering to measure MW, one needs a series of standards of equal
concentration but varying and known MW. A calibration curve of intensity of scattered
light vs. weight average MW is plotted. The intensity of light scattered by a solution of the
same type of polymer at equal concentration is measured and its weight average MW is
read from a graph.

2. Ultracentrifuge: After centrifuging a solution of the polymer at high speeds for several
weeks, a concentration gradient is established with larger particles in the lower layers
of the solution. The concentration of polymer at various depths is then determined by
optical methods.
3. Gel Permeation Chromatography: (size exclusion chromatography). A crosslinked
porous, polystyrene packing ('gel') separates polymer molecules based on their size.
The flow of smaller polymer molecules is slowed down as they diffuse into the pores
of the gel while larger molecules move through the column more quickly. A suitable
detector (e.g. photometer, conductance, etc.) indicates the relative concentrations.

Ostwalt viscometers are used to measure relative viscosity

of dilute solutions of polymers. The viscosity is directly
proportional to the polymer chain length. To determine
the viscosity average MW of a polymer, one must first
prepare a series of standards of equal concentration (w/v)
but varying and known MW. The viscosity of a solution of
the same type of polymer at equal concentration is
measured and its viscosity average MW is read from a
graph.

Viscosity

Viscosity Average Molecular Weight:

viscosity avg.
MW

Number-Average Molecular Weight:

The number-average molecular weight, Mn, is the common arithmetic mean calculated by
counting the number of molecules (or moles) of each particular size, summing these, and then
dividing this sum by the total number of molecules (or moles), just as the average score in a
series of organic tests is calculated by adding all scores and dividing by the number of tests.

Mn

N 1M1 + N 2 M 2

N1 + N 2

N M
N
i

ni M i

where

Ni = # moles polymer with molecular wt. = Mi

ni = mole fraction polymer with molec. wt. = Mi
Weight-Average Molecular Weight:
In the calculation of Mn , the molecular weight of each species was multiplied by the mole
fraction of that species. Similarly, in the calculation of weight-average molecular weight, Mw ,
the molecular weight of each species is multiplied by the weight fraction of that species.
M w wi M i

W M

W
i

N M M

NM
i

NM

NM
i

where

Wi = wt. of polymer with molecular wt. = Mi

wi = weight fraction of polymer with molec. wt. = Mi
Example: A polyethylene sample contains 50 mol % of a species with molecular weight of
10,000 g/mol and 50 mol % of species of molecular weight 20,000 g/mol.
Calculate Mn, Mw, DPn, and DPw. Note that
DP = ( M/weight of a mer)
Ans: Mn = 15,000, Mw = 17,000, DPn = 540, DPw = 610

Both Mn and Mw are theoretical concepts and are not calculated in the manner of the previous
example. The example serves to illustrate the concepts. The reason for introducing different
measures of average molecular weight is because the various analytic techniques described
above give different values for average molecular weight.

Mn is obtained by end-group analysis and by colligative properties. These methods

measure the number of molecules in a sample.

Mw is obtained by light scattering techniques (photometric methods). Light scattering is

dependent upon the size (weight) of particles.

Polydispersity Index:
For all polydisperse polymers Mw is always greater than Mn . Only in the case of a
monodisperse, where all molecules are the same size, does Mw = Mn .

The ratio Mw / Mn , called the polydispersity index, is a measure of the MWD of a polymer.
The farther the polydisperse is from 1.0, the wider the MWD of a sample. Some typical
data is given in the following table ...
Polymer

Mn ( 10-3)

Mw ( 10-3)

Mw / Mn

alkyd resins

25 - 50

50 - 200

2-4

epoxy resins

0.35 - 4

0.35 - 7

1.0 - 2.5

acrylic polymer

25 - 350

40 - 600

1.1 - 1.8

polybutadiene

2 - 50

2.1 - 52

1.05 - 1.1

A large polydispersity index indicates a polymer is more deformable (reduced stiffness,

increased toughness) and of lower melt viscosity than a sample of the same polymer with
a lower index; the presence of short chains acts as a plasticizer by reducing entanglement
of the larger polymer chains.

Viscosity-Average Molecular Weight:

Because viscosity measurement of a polymer solution is comparatively simple, this method is
commonly performed and the molecular weight determined by this method is called viscosityaverage molecular weight, Mv . Values of Mv always lie between Mw and Mn and are usually
10 to 20% below Mw .

CHM 605
Part 11
POLYMER
TEST
QUESTIONS

POLYMER REVIEW
1.

2.

3.
4.
5.
6.
7.
8.
9.
10.

11.

12.
13.
14.
15.
16.

17.
18.
19.
20.
21.

Polymer history: Complete the following ...

a) ....................................... is a polymer used by the Mayan Indians of S. America
b) ....................................... was the polymer first used as an ivory replacement
c) ....................................... was the first thermal resistant polymer, i.e., pot handles
d) ....................................... is known as the Father of polymer chemistry.
State, define or explain in as few words as possible ...
a) Staudingers Macromolecular
f) mer
Hypothesis
g) mesomer
b) homopolymer
h) oligomer
c) copolymer
i) high polymer
d) terpolymer
j) degree of polymerization
e) ionomer
Using A and B for monomers, show & name 4 different arrangements of comonomers in copolymers
List the 3 most important feedstock monomers for making polymers.
List 9 groups of polymers classified according to end use and 1 chemical name of a polymer for each.
Sketch the appearance of linear, branched and crosslinked polymer chains.
Give one example each for monomers with functionality of 2, 3, and 4
State 4 characteristics each for thermoplastics and thermosets.
Name 3 thermoplastics and 3 thermosets.
Explain in as few words as possible ..
a) amorphous polymer
c) glassy state
b) crystalline polymer
d) tacticity
Sketch polymer chains in their planar zigzag conformation showing ...
a) isotactic polypropylene
b) syndiotactic polystyrene
c) atactic poly(vinyl chloride)
For each polymer in question 11, state whether it is amorphous or crystalline.
Sketch cis- and trans-1,4-polybutadiene to show their stereochemistry.
Give names or draw structures of polymers using IUPAC and common nomenclature for all examples
covered in class.
Write the 7 SPI recycle symbols and the corresponding chemical names and abbreviations..
Explain briefly ..
a) crystallite
c) 1st order transition temperature
b) glass transition temperature
d) 2nd order transition temperature
Name and draw the structures of 2 commercial plasticizers.
Explain briefly, the function of a plasticizer with respect to its physical properties.
List 2 polymers with low Tg and 2 with high Tg
State if these polymers have high or low Tg and why: PS, isotactic/atactic PP, PVC, and PE
Answer with or . Increasing the number of branches in a polymer
a) causes the crystallinity to .......
b) causes the density to .......
c) cause the melting point to .......
d) causes the tensile strength to .......

22.
23.
24.
25.

Give the approximate density and melting point of LDPE and HDPE.
What is the lowest DP at which the melting point of PE exceeds 100 C?
What is the DP of PE with the formula C200H402? What is the MW of PE given DP=3000?
Calculate the DP of PP with avg. molecular weight of 200,000

26. List 6 methods of determining average molecular weight of a polymer and state whether the method determines
number-average, weight-average, or viscosity-average molecular weight.
27. Calculate the average MW of a polymer using data re: any of the colligative properties as discussed in class
28. Arrange these 3 molecular weights in decreasing magnitude as determined on the same sample of polymer.
29. Using a simple graph (with labeled axes) explain the difference between a polydispersity index of 1.1 vs. 4.
30. What effect does a high polydispersity index have on a polymers physical properties?
31. List 4 non-catalytic methods and 3 catalytic methods of polymerization
32. Name the 3 main types of polymerization and name 1 example of a polymer for each.
33. By means of equations show the complete cycle of free radical polymerization of a vinyl polymer (e.g., PE, PP,
PVC, PTFE, PS) (Instructors choice on a test). Include termination by combination and disproportionation, chain
transfer with solvent (e.g., CCl4), polymer, and chain transfer agent.
34. Give the formula and name of 1 chain transfer agent.
35. State the effect avg. molecular weight on...
a) adding chain transfer agent
b) adding a very small quantity of initiator
36. Give the formulas or structures of, and state the names of 2 common free radical initiators for free radical
polymerization. Show the mechanism of their dissociation and give the formula/structure of their products.
37. List 2 initiator accelerators (i.e., redox initiators)
38. Give the name and structure of 2 free radical inhibitors. Why are they needed?
39. Use resonance structures to show and explain why one of these inhibitors is effective.
40. What are the cause, effect and mode of prevention of the Tromsdorff-Norish Effect?
41. List 3 dienes which can be free-radical polymerized and draw their structures.
42. Show the mechanism of initiation and propagation of free radical polymerization of a diene (1,4 or 1,2)
43. Draw structures of 3 monomers which can be polymerized a) cationically, b) anioinically
44. Draw resonance structures to show how styrene can stabilize either a benzylic cation, anion or free radical
(Instructors choice on test).
45. Show the mechanism by which water can deactivate a cationic (or anionic) end group.
46. Show the mechanism of initiation of anionic polymerization of vinyl chloride with methyl lithium (or with Li
metal, or Li + naphthalene). Then show one propagation step.
47. Show the mechanism by which functional end groups can be created by termination with carbon dioxide and with
ethylene oxide.
48. Write equations to show cationic polymerization of isobutylene including its initiation with H2SO4 or with a Lewis
acid catalyst (e.g., BF3, AlCl3, SnCl4, ZnCl2).
49. List the approximate conditions (temp., pressure) of the high pressure PE process and the Ziegler-Natta Coordination
Process. State the type of polymer produced by each and list 2 applications for both types of PE.
50. What is the catalyst commonly used in the Ziegler-Natta process?

51. What is meant by propagation from the root vs. propagation at the tip? Which process causes each
of these kinds of propagation?
52. List examples of 4 different types of polymers that are polymerized by the step-growth method.
53. Show the mechanism of step-growth polymerization of poly(ethylene terephthalate) (or Nylon 6).
54. Name 2 subdivisions of step-growth polymerizations and briefly state their difference.

55.
56.
57.
58.

Show the polymerization of HMDI and HMDA (one step) and name the type of polymer formed.
Draw & name the reagents & product of polymerization of 1,4-diisocyanotobenzene and 1,2-diaminoethane.
Show the mechanism by which ethylene oxide is polymerized.
Draw and name the polymer produced from -caprolactam

59. List the ingredients, advantages, and disadvantages of bulk polymerization and 3 polymers commonly produced
by this technique.
60. Repeat the previous question for Solution, Suspension and Emulsion polymerization.
61. Given that the planar zigzag conformation of extended chain PE has a contour length of 2.55 Angstroms, calculate
DP and the contour length of chain extended molecules of PE with an average MW of 750,000.
62. State briefly why solution crystallized polymer crystals are brittle.
63. Give the name of the following ...
a) ................................................................... crystals which form during quiescent crystallization from the melt.
b) ................................................................... the units which hold polymer crystals together.
c) ................................................................... an industrial method of stress induced crystallization.
d) ................................................................... the maximum draw ratio for polyesters and polyamides
e) ................................................................... the maximum draw ratio for HDPE
f) ................................................................... the name for localized reduction of cross sectional area of a thermoplastic
under tensile loading.
64. Sketch the main components of a melt spinning unit and label its parts.
65. State 2 important changes that occur during stress-induced crystallization to increase stiffness and strength.
66. Name 3 engineering resins and 3 specific applications for such resins.
67. Name 3 high performance resins and the physical properties that set them apart.
68. Briefly state the meaning of a failure test and list 6 examples.
69. Calculate the stress (in SI and British units) when 2.20 103 lb. force is applied to a polymer specimen that is
1/8 thick and wide.
70. Calculate (to 3 sig figs) the proportional and % strain of a specimen with an original length of 3.000 in. and a final length
of 3.002 in.
71. Given various stress strain curves, label the following points; rupture strength, tensile strength, ultimate strength,
elastic limit, yield strength, and proportional limit.
72. Calculate the modulus of compressive elasticity, stress, proportional strain, and toughness for the linear initial stress
strain data from a tensile test given the following data ... original specimen width = 0.5, thickness = and original
length of 2.000 in.; final length at 9.00 103 lb. load is 2.00165 in. Report in SI units to 3 sig figs.
73. Name the ultimate property that the notched Izod test measures.
74. Given a series of stress strain curves, classify the polymer as soft and weak, soft and tough, etc. and name one
polymer that demonstrates this.
75. Briefly explain how polymer hardness is measured.
76. Elongation under long-term loading is called ...................................................................
77. List 5 reinforcing additives.
78. List 1 toughness modifier.
79. Name 2 plasticizers.
80. Name one of each of the following stabilizers; thermal stabilizers, antioxidants, UV absorbers.
81. Name 2 colorant additives.
82. List 5 inert fillers and 3 reasons for adding them.
83. Name 2 polymers whose maximum use temperature is close to 300 C.
84. Give the maximum use temperature of Nylon-6,6 and PET (see Table V on p. 61).
Give the maximum use temperature of LDPE and HDPE

85. Draw the mechanism for the synthesis of a polyamide by reaction of: an amine + acid chloride, amine
+ acid anhydride, amine + carboxylic acid, ring opening of a lactam
86. Write the formulas and names of the monomers and formulas of the polymers for the following
polyamides... nylon 2, 4, 5, 6, 12, 6-6, 6-12, Kevlar and Nomex
87. Using equations, show the polymerization of nylon 6-6 from 2 different sets of starting reagents.
88. List 4 different, specific applications of aliphatic nylons and 4 specific applications of Aramid fibers.
89. Write the complete mechanism of acid catalyzed Fischer esterification.
90. Write the mechanism of esterification from acid chloride or acid anhydride (Instructors choice on
test).
91. By means of an equation, show the formation of PET by any of the four polymerization methods, i.e.,
direct esterification, ester exchange, using an acid chloride, or using an acid anhydride (Instructors
choice on test). Also show the byproduct formed.
92. Write equations to show the polymerization reaction that forms...
a) PC (also name the reagents) and show by products formed
b) glyptal resin (you need only show the first steps)
c) an oil modified alkyd for paints (you need only show the first steps)
d) an unsaturated alkyd for FRP (you need only show the first steps)
93. List 4 different, specific applications of PET
94. List 4 different, specific applications of PC
95. Write equations to show the polymerization reaction that forms poly(dimethylsiloxane) or
poly(diphenylsiloxane) (Instructors choice on test). Show the byproduct (condensation product)
formed.
96. List 4 different, specific applications of silicones.
97. Write the names, symbols, and numbers of the 7 recycle groups for plastics as per the Society for
Plastics Industry (SPI).
98. List 4 different, specific applications of PTFE
99. Write the chemical formulas and names of CTFE, FEP, and PVF2 polymers.
100. Compare silicone elastomer, nylon 6 resin, PC resin, and PTFE resin and choose the 1 which best fits
each of the following descriptions....
a) highest s.g. (& give approx. value)
l) highest crystallinity (& give approx.
value)
b) highest Tm (& give approx. value)
m)
lowest crystallinity
c) lowest Tg (& give approx. value)
n) highest optical clarity
d) lowest % HOH absorption (& give value)
o) lowest optical clarity
e) highest % HOH absorption (& give
value)
p) highest H-bonding
f) highest lubricity
q) least H-bonding
g) highest chemical resistance
r) greatest flexibility
h) least chemical resistance
s) lowest Tensile strength resin
i) highest UV resistance
t) highest impact resistance resin
j) best electrical resistance
u) resin with greatest cold flow
k) greatest aromatic content
v) most expensive
w) most difficult to process

101. Write a formula or chemical name (your choice) that corresponds to each of the following trade
names: Fortrel, Dacron, Terylene, Mylar, Kevlar, Nomex, silk, Lexan, FRP, RTV caulking, silicone, Kel F,
Viton.
102. Draw the mechanism of resole formation using sodium phenoxide and formaldehyde.
103. Draw the mechanism of novolac formation using phenol and formaldehyde.
State 4 important properties of phenolics and then 4 applications that result from these properties
104. Draw the mechanism of epoxy prepolymer formation from bisphenol-A and epichlorohydrin.
105. Name the type of hardener most commonly used for epoxies.
106. List 4 important properties of epoxies and state 4 applications, which result from these properties.
107. State briefly, the sequence of operations in injection molding, extrusion, and/or transfer molding.
108. Name one type of plastic and one example of a product made by each of these processes.
109. Given a diagram of an injection molding machine, label its parts.
110. Briefly explain what is meant by the following terms: blow molding, parison, compression molding,
calendering, sprue, runners, gate, parting line and flash
111. Name 2 polymers that float in water and 2 which sink in water.
112. Name 2 polymers that continue to burn when removed from a flame.
113. Name 2 polymers that are self extinguishing.
What element(s) does the Beilstein test identify in a polymer?