You are on page 1of 51

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 “mackintosh’s” 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,

a

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. England’s 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
England’s 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

b

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 Payen‘s 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

c

this was before Thomas Alva Edison (1847 – 1931). On gentle heating. the fully synthetic Bakelite plastic.. tradenamed celluloid. John Wesley Hyatt was granted a patent for the use of camphor without castor oil and without alcohol. which is manufactured from phenol and formaldehyde. In 1884. occasionally with unexpected side effects: Billiard players were literally shooting pool since the surface coating exploded on very hard impacts. English and American patents of Daniel W. The new "Chardonnet silk" was exhibited in 1889 at the Paris World Exhibition. elastic objects. 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. At about the same time. 9). This fame is claimed by a later invention. i. for example. hitherto made from ivory. two years later. Chemist Schonbein knew this of course and in order to prevent greater harm. camphor. about $100. Many pool balls were however not manufactured from cellulose nitrate/ camphor.000 in today‘s money. and dyestuffs. which is impossible to do with cellulose. Cellulose nitrate is quite different from cellulose. Cellulose nitrate first led to the discovery of plastics (see below). Before Hyatts’s invention. It dissolves in many organic liquids in which cellulose is insoluble. 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”.1924) was looking for a replacement for natural silk since the flourishing French silk industry was threatened by the mulberry spinner pest. The time was ripe for a technological breakthrough which is usually the result of the ignorance of laymen and the hyperbole of experts. manufacturers tried to smooth the surfaces by coating them with cellulose nitrate. 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. which in turn caused some in the Wild West to draw the revolver … Hyatt’s invention won the $ 10.called “agua regia“ (royal water) by the alchemists: It dissolves almost everything. the commercial production started. he found a way to spin fibers from cellulose nitrate solutions and to convert the flammable cellulose nitrate fibers into non-flammable cellulose fibers.3 The First Plastics Cellulose nitrate differs from cellulose not only in flammability and solubility but also in another aspect. Schonbein had unintentionally converted cotton into gun cotton. they caused a lot of excitement and even earned a gold medal. Billiard (pool) balls of ivory often have slightly uneven surfaces and they track erratically. 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. naturally growth elephant’s teeth. 2. Many other processes and fibers followed (see Chap. a Frenchman. A solution in a mixture of alcohol and ether produces. These completely new and unexpected properties inspired other inventors. he had performed a chemical transformation of cellulose into cellulose nitrate often also called “nitrocellulose”. Count Louis Marie Hilaire Bemigaud de Chardonnet (1839 . a sticky liquid which can serve to cover small wounds and this collodium. Spill who used alcoholic solutions of camphor instead were equally unsuccessful. The products were modestly called "Parkesite”. Alexander Parkes found in 1862 a method for the easy processing of cellulose nitrate after the addition of castor oil. the first liquid sticking plaster. These were exactly the properties need for billiard balls. he took a piece of fabric to wipe it off. d .e. then to the invention of man-made fibers. even the otherwise unassailable gold metal. The mixture of cellulose nitrate and camphor could be shaped at moderate temperatures to hard objects with very smooth surface. it can be molded into hard. That fabric happened to be the cotton apron of his wife. In 1869.000 reward for better billiard balls. was invented.

It is estimated that world demand for ivory required the annual killing of 100. ‘plasticos”=to shape. In 1906 he heated various phenols with formaldehyde and produced insoluble. Materials with this property are called “themoplastics” (Greek: “themos”=warm. Bartholomaus Schobinger. They can be reshaped many times on renewed heating. The mass is finally compacted in molds under the addition of dyestuffs. Galalith is still used today for haberdashery since it is easy to dye in beautiful colors. Wilhelm Krische and Adolf Spitteler. whey is removed from the curds by pressing and the remaining substance is kneaded in hot water until all fats are removed. on the other hand. The formulation was however forgotten until the American Emery Edwin Childs was granted a patent for the production of plastic masses in 1885. called “galalith". Phenolic resins differ from cellulose nitrate especially in one property. The resulting phenolic resins were resistant against solvents and heat and these “Bakelites” were recognized in 1909 as excellent electrical insulators. The latest statistics discloses that in 1983 Germany imported 32. The new plastics saved annually the lives of several tens of thousands of elephants. This process is purely physical. Italy and India. to name a few? Another early plastic used casein. The import of Asian ivory (but not of African ivory carvings etc. Celluloid.000 elephants during the period 1860-1870. Cellulose nitrate can be molded at elevated temperatures to articles which retain the shape after cooling.The first plastics contributed considerably to wildlife protection since far less elephants were killed for their ivory. porcelain powder. 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. This amount corresponds to 9000 elephants since a pair of elephant tusks weighs about 45 kg (100 lbs). A short excursion into some basic chemistry is thus necessary before we can proceed with tales of tall molecules. 580. etc. More than 8000 elephants died in 1864 just to cover the English consumption of ivory. and haberdashery. Baekeland who lived in the United States.e. Plastics with this property are called "thermosets". hard masses. The difference between phenolic resins and cellulose nitrate is due to their different chemical make-up.) is illegal in the United States but what about the use of ivory in other countries such as England. to form). the white material from skim milk. Ebonite and Galalith are semi-synthetic products since they originate from natural products which are then chemically converted into new compounds. They became one of the foundations of the modem electrical industry. the deformation under heat.696 kg tusks. i.000 kg (880. retain their shape upon renewed heating to the original processing temperature. the United States imported more than 400.388 carvings. in 1897 to an artificial horn which the German inventors. "milk stone” (Greek: gala = milk.. lithos = stone). In this process. they cannot be reshaped again by heat.000 lbs) of ivory which was used not only for billiard balls but also for piano keys. the recipe is said to come from a Swiss merchant. knife handles. The chemical reaction of this material with formaldehyde led. however. In 1909 alone. A “pretty horn" (“schon hom”) from skim milk was already described by the German Benedictine monk Wolfgang Seidel (1492»1562). and 1767 kg of other ivory which translates into at least 2100 animals. Those who still remember their high school chemistry may of course skip the next chapter. The first fully synthetic plastic was invented by the Belgian Leo H. Even people were protected: An estimated 4000 hunters died while hunting these large herbivorous animals. Phenolic resins. e .

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

urea-formaldehyde resins 1931 poly(methyl methacrylate) plastics Neoprene synthetic rubber 1936 poly(vinyl acetate) and poly(vinyl butral) 1937 polystyrene (PS). poly(vinylidene chloride) 2 . cellulose acetate plastics 1929 polysulfide (Thiokol) rubber...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). styrene-butadiene (SBR) 1938 Carothers produced nylon 66 fibers 1939 melamine-formaldehyde resins.

aromatic polyamides (Kevlar). fluorocarbons. 1980's ultra high molecular weight polyethylene fibers (Spectra) 3 .1940 butyl rubber (US) 1941 low density polyethylene WW2 silicones. 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. polyurethanes. polycarbonates 1959 synthetic cis-polyisoprene 1960 ethylene propylene rubber 1960’s cyanoacrylate adhesives.

000 Answer: 280.. The number is often enclosed in the triangular arrows recycling symbol. which is usually stamped on the bottom of the product.Vinyl / Poly(vinyl chloride) (PVC) ………………………………… 4 LDPE . . i. i.Manufacturer's Labeling Code: The composition of an increasing number of plastic products is identified using the SPI (Society for Plastics Industry) recycling code. -(CH2CH2)-10.000g Calculate the DP of PE with MW = 28. Examples 1 PETE – Poly(ethylene terephthalate) ………………………………… 2 HDPE .e. 1mol of 100mers = 28g × 100 = 2800g Calculate the MW of PE with average DP of 1000..000. Calculate the MW of PE with average DP of 100.Low Density Polyethylene ………………………………… 5 PP – Polypropylene ………………………………… PS – Polystyrene ………………………………… Other ………………………………… 6 7 Poly(ethylene terephthalate).High Density Polyethylene ………………………………… 3 V .e. -(CH2CH2)-100 Soln: 1mol mers = 28g. 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..000g Calculate the MW of PE with average DP of 10. The code is as follows.000g Solution: 28.e. DP = 1000 4 . i..000g/(28g/mer) = 1000mers. -(CH2CH2)-1000 Answer: 28.

and -CF2-.000. Ionomers with many ionic groups are used as polyelectrolytes for dispersing agents and flocculants.e... is used to make each type or family of polymer. Molecular Weight (g/mol) Homopolymers are polymers made by polymerizing only one kind of monomer.Polymers are chain-like molecules of high molecular weight (also called ‘macromolecules’). MW > 106. comonomers. (CF2-CF2)n. Copolymers are made by polymerizing > 1 type of monomer.g... i. This is done to modify the properties of a coating. “DP” Note that for polymers formed from symmetric monomer units such as PE.. 5 .g.000 g/mol depending upon how polymerization took place.. (Teflon). 1000 to > 1. ‘Poly’ means ‘many’ and ‘mer’ means ‘part’. 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. and auto body panels... For example. ethylene and propylene comonomers can be polymerized together forming a polyethylene/polypropylene copolymer . Polymers are built up from smaller simpler molecules called ‘monomers’. The degree of polymerization varies from molecule to molecule in a sample and varies from sample to sample. called the ‘degree of polymerization’.. Oligomers are short-chain polymers ('oligo' = few) with 50  DP  3. It is not uncommon for coatings to be formulated with 3 or 4 comonomers. A monomer is literally ‘one part’ of the many parts in the polymer. That is to say that in a given sample of # polymer. Ionomers are polymers with ionic groups such as carboxylate salts. respectively but by convention both methylene groups (or difluoromethylene groups) originating from the ethylene (CH2=CH2) or tetrafluoroethylene (CF2=CF2) monomer are shown. or combination of monomers. (CH2-CH2)n. or poly(tetrafluoroethylene). Acrylonitrile-butadiene-styrene (ABS) is a terpolymer with high impact resistance used for residential DWV piping. e. 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. e. comprised of repeating structural units joined by covalent bonds. Terpolymers are copolymers comprised of 3 comonomers. the simplest repeat units would be -CH2. polyethylene is made by polymerizing ethylene . not all molecules are of the same length and same molecular weight. e. A different monomer. i. polyethylene. The average molecular weight of polymers varies widely.e.g. High Polymers are very high or ultra high molecular weight polymers.

.Arrangement or comonomers in copolymers: 1. Propylene and butadiene. In N.. the highest volume organic chemical in North America (and the fourth highest industrial chemical) is also the largest volume monomer for plastics. the other two largest monomers for plastics. Alternating 3. 1 s. ethane from natural gas is steam cracked at 700 C for ca. are also produced as by products polyethylene + chlorine + benzene ethylene vinyl chloride styrene poly(vinyl chloride) polystyrene + oxygen ethylene oxide. C2H4. 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). C2H4.. then phenol & acetone acrylics urethanes phenolics polybutadiene butadiene + styrene SBR rubber + chlorine chloroprene + ammonia hexamethylene diamine neoprene Nylon 66 6 . the C5-C12 fraction (naphtha) of crude oil is cracked to produce both C2H4 and gasoline. Block copolymers 4. ethylene glycol polyethers polyesters polypropylene + ammonia acrylonitrile propylene + oxygen + benzene propylene oxide cumene. C2H6  C2H4 + H2 + other HC's In Japan and Europe. 37  109 lb/yr in the USA. two of the largest volume organics. Random: 2. cost ca. Graft copolymers Feedstocks for Polymers: Ethylene. America.

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

with 1 double bond can bond to 2 other molecules so it has a functionality of 2. waste materials can be recycled (10-20 ).e. soluble in appropriate solvents 3. Butadiene. but they gradually degrade after repeated cycling Thermosets such as epoxies. Ethylene glycol.. polystyrene. 1.g. Crosslinked (or Network): Functionality: Carothers defined functionality as the number of bonds a monomer can form. CH2=CH2. e. melt when heated 4.. Linear: 2. has a functionality of 2 What is the functionality of propanetriol. with 2 hydroxy groups. once polymerized. HOCH2CH2OH.. Thermoplastics exhibit the following properties .. Classification of Polymers as Thermoplastic or Thermoset: Linear and branched chain polymers are thermoplastic. i. i. i. Ethylene. exhibit the following properties . e.e.don’t dissolve but may swell 3..cannot be melted (heat resistant) but will decompose at high enough temperature 4. vinyl chloride. have a functionality of at least 2.g. styrene (vinyl benzene). tires.. polyethylene.Classification of Polymers Based on Structure: Polymer chains are linear. with 2 double bonds can bond to 4 other molecules so it has a functionality of 4. rubber. All monomers must be able to form at least 2 bonds per molecule. insoluble in solvents . phenolics.... 1.. fusible. 1. infusible . foams) 8 . This is true for most vinyl compounds. they are linear or branched 2. Network polymers (and some branched) require monomers with a functionality of at least 3.e. HOCH2CH(OH)CH2OH ? Linear polymers (and some branched) are formed by monomers with a functionality of 2. PVC. CH2=CH-CH=CH2. etc. they are crosslinked (or network) polymers 2.. otherwise the molecules could not polymerize. branched or cross-linked . Branched: 3. they cannot be reprocessed (or only with difficulty.

Calculate the molecular weight of a 10 pound bowling ball polymer. vaporizing. adsorption. used for pocket combs and bowling balls. PE (nonpolar HC) = ~110 C Nylon 66 (polar. covalent bond strength governs photochemical and thermal stability (decomposition). e. dissolving. -HN-. however the major portion of polymer in a tire or bowling ball is really one molecule. polar.. Natural rubber consists mostly of a linear polymer that can be crosslinked to a loose network by reaction with 1 to 3% sulfur. For example. -HF-. Rubber is a good example. and flow involve the making and breaking of intermolecular 'bonds' so that molecules can move past one another or away from each other. (ans. We are accustomed to thinking of molecules as submicroscopic. The same polymer reacted with 40-50% sulfur is 'hard rubber'.Note that only thermoplastics can exhibit plastic flow and solubility because they are composed of large but singular (unconnected) molecules. = 2. insolubility and infusibility. Polymers with polar functional groups. a tight network polymer. secondary forces determine most of the physical properties we associate with specific compounds.g. polyaramid) = ~500 C 9 . i.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). Kevlar (a tightly packed. This is because all the separate molecules in the tire were connected to one another by sulfur cross-links during 'vulcanization'. sulfur-vulcanized rubber is more likely to degrade at the comparatively weak -S-S. On the other hand.) have strong intermolecular forces and have relatively high softening temperatures. In general. particularly with H-bonding (-HO-.bonds (83 kcal/mol).e.. Thermosets are composed of an infinite network of bonded molecules which cannot be separated without breaking covalent bonds. 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. deformation. Melting.bonds (51 kcal/mol) than at the strong -C-C.

7 .) 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 . can become large (up to 10 Kcal/mol) in very large molecules such as high molecular weight polymers. O. the weakest of all intermolecular forces.5 .5 .pair 35-250 H-H cations to delocalized e-'s 18-240 Fe + Intermolecular Forces: (Forces between chemical species.. 10 . H Na+ I d+ (F..140 dipole charges 1-6 .5 polarizable eclouds 0. or O) 2. H O . H O .. H Br2 Cl Cl Ne London Forces. H Fe+3 H Cl Ne I Cl .4 dipole charge to polarizable e.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.01 – 1 Cl ..2.10 ion charge to polarizable ecloud 0. or N bond to H) to (F. N. e.g. high molecular weight polyethylene.cloud 0. H O .

For polymers. PS. intermolecular and intramolecular forces Intramolecular forces (covalent bonds) hold the mesomers together in a polymer chain.4'-b-glycosides n 11 ..4'-O-(b-D-glycopyranoside) polymer CH2OH 4' Cl Cl Cl b Cl CH2OH . a 1. OH b-D-glucopyranoses 1.g. O Cl Cl Cl O OH OH 1 OH Cl O .g.. 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.) cellulose.Classification of Polymers by Chemical Makeup The forces that hold polymers together can be divided into two kinds. ‘induced dipole – induced dipole’ forces (London Dispersion forces) in non polar polymers (e. PVC.. O . ‘dipole-induced dipole’ & ‘dipole-dipole’ forces in polar polymers (e.. O ... etc. PP) 2. secondary forces include: 1. PE. cellulose.

poly(vinyl acetate) – Elymers glue) O O C O C O C O- O- O- C O C O C O- O- O- In network polymers. Sulfur is often used to crosslink unsaturated thermoplastic polymers..induced dipole’ in ionomers (e.3.g. ‘ion-dipole’ & ‘ion. crosslinked chains are held together by both intermolecular and intramolecular forces.4-polyisoprene (natural rubber) with sulfur crosslinks Describe the type of intramolecular and intermolecular forces in polyamides like Nylon O H H N N H O N O H N O 12 . CH3 CH3 CH3 S S S6 S6 S isoprene (latex from rubber tree) CH3 CH3 CH3 S CH3 1.

These are best visualized by looking at the polymer in its planar zigzag conformation. CH3 CH3 CH2 CH propylene ( CH2 C) n H polypropylene In the repeating unit. If the polymer chain contains carbon atoms with two different substituents. syndiotactic PP has a regular alternation of pendant groups. The regularity of this arrangement allows orderly packing necessary for high crystallinity. every other carbon is asymmetric. The disordered state may be glassy and brittle or it may be molten and viscous or it may be rubbery. In general. the carbon is asymmetric. since the two parts of the chain with which it is connected are different also.Classification by Physical State: Polymers may be partially crystalline or completely disordered (amorphous). using the terminology of stereochemistry. isotactic PP has each pendant methyl group on the same side of the chain. Such asymmetric carbons can exist in two different spatial configurations which are not interchangeable in stereoisomers without breaking covalent bonds. (the mer). Vinyl polymers are formed in any of three different configurations or 'tacticity'. Consider the linear polymer. This arrangement can also produce high crystallinity and the planar zigzag conformation is sterically unhindered. so that crystallinity decreases. Branching interferes with the orderly packing of molecules. that is all d or all l. 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. 13 . Isotactic polymers form helices to alleviate steric strain. polypropylene. Three tacticities of PP can result.

flexible rubber 14 ..4-polybutadiene. m. Again.p. with the aid of special catalysts. etc.4-polybutadiene Trans-1.3-butadiene can be polymerized to either the cis or trans polymers (cis.or trans-1.. So it is desirable to be able to control the stereochemistry and hence the crystallinity during polymerization. tensile strength.4-polybutadiene in this example) .4-polybutadiene produces a superior. it was difficult to produce synthetically any structure except atactic. Cis-1. Until the advent of coordination complex catalysts. Increasing the crystallinity of a polymer often improves its physical properties.e.. i. produces a stiff inferior rubber.Random placement of methyl groups gives PP an atactic structure which cannot allow a highly crystalline packing arrangement. monomers like 1.. A second type of stereoisomerism in polymers is the cis-trans variety. CH2=CH-CH=CH2 1. when vulcanized.3-butadiene  ( CH2-CH=CH-CH2 ) 1.

CHM 605 Part 2 POLYMER NOMENCLATURE 15 .

parentheses are also added.. Common names based on the monomer: Add 'poly' as a prefix to the monomer name. 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. For example.Nomenclature of Polymers: As in the case of organic chemistry in general. Trade names and acronyms: memorized. e. is named and then prefixed with 'poly'. 16 . vinyl chloride polymerizes to poly(vinyl chloride) 2. The three methods of naming polymers are .g. Similarly. ethylene polymerizes to polyethylene. 1. CRU. the nomenclature of polymers is not fully systematic and the actual nomenclature is a mixture of common and IUPAC names.. (CF2-CF2)n is named poly(difluoromethylene). sometimes called the constitutional repeat unit. These are historical and industrial and must be 3. For complex monomers. Nomenclature based on the IUPAC system: The simplest repeat unit in the polymer. (CH2-CH2)n is named polymethylene since the simplest repeat unit is actually -CH2-. For example.

c = common.Name the following polymers. I = IUPAC. )n ( Cl c: poly(vinyl chloride) I: poly(chloroethylene) )n ( O O) ( n OH c: I: F F F F F F F F F F F F F F F F c: I: Cl Cl Cl Cl Cl Cl c: I: 17 .

O O n n c I n c I O O O c I O c N H n I 18 .

(PS) Styrofoam vinyl acetate poly(vinyl acetate). (PVA). Tygon tubing vinylidene chloride poly(vinylidene chloride) Saran wrap tetrafluorethylene poly(tetrafluoroethylene).). (PVC) Vinyl. Trade name polyethylene (PE). (PP) Herculon upholstery. vinyl chloride poly(vinyl chloride). (LDPE). (HDPE) polypropylene. (PVAL) . (PTFE) Teflon styrene polystyrene. (PVAc) ‘Elymer’s Glue’ poly(vinyl alcohol).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 n Common Name (Abbrev.

(PAN) Orlon fibre acrylic acid poly(acrylic acid) methyl methacrylate poly(methyl methacrylate).4-poly(1.3butadiene Neoprene polyisoprene. Lucite. Trade name polyacrylonitrile.3-butadiene) 1.3butadiene polychloroprene.3-butadiene cis-1. Delrin 20 . (isoprene) cis-1. (chloroprene) 2-methyl-1.3-butadiene trans-1.Monomer Structure Monomer Name acrylonitrile Polymer Repeating Unit Common Name (Abbrev.3-butadiene) 2-chloro-1. Perspex 1.4-polyisoprene = Gutta Percha ethylene oxide poly(ethylene oxide) = poly(oxy-ethylene) Carbowax formaldehyde polyformaldehyde.4-poly(1.).4-polyisosprene = latex rubber and trans-1. (PMMA) Plexiglas.

CHM 605 Part 3 PHYSICAL PROPERTIES OF POLYMERS .

If the cooling was rapid. 1. a thermoplastic is heated above its melting temperature. thermoset (crosslinked) polymers inhibit rotation 3. partly crystalline.g. This is the 'crystalline' state. amorphous poly(ethylene terephthalate). their crystals scatter light. 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. 95% crystalline High Density Polyethylene (HDPE).. molecules do not have time to arrange themselves in an ordered (crystalline) manner and are trapped in a disordered. the presence of solvents allow rotation below the normal solidification temperature As a result. e.e. This liquid state is a 'melt'.. . during these rotations. i. for pop bottles and poly(vinylidene chloride) for Saran Wrap. i. entangled state. MW is a variable 4.g. e. polymers may be completely amorphous. When a polymer. however. (LDPE). Three extreme conditions of physical state are possible . If cooled slowly from the melt (or stretched while cooling) the chains of polymer may align themselves into a regular crystallatice.. the bond angles and distances remain fixed. for plastic bags is translucent.  Amorphous polymers tend to be transparent. the chain might assume an infinite number of conformations in space.g. Each of these is a simplification. Completely free rotation in a liquid state:.e. 55% crystalline Low Density Polyethylene. its continuously wriggling molecules can slip past each other...  Crystalline polymers are opaque.. Other factors modify the physical state of a polymer. 1. e. e. (PET). branching interferes with orderly packing 5.g. longer chains experience greater intermolecular attraction and entanglement per molecule than shorter chains of the same polymer. the presence of highly polar groups resist free rotation 7.. It is amorphous. No rotation in a tangled solid state. or wholly crystalline. 2.g. The higher the temperature. 3. at some sufficiently low temperature. the presence of double bonds in the chain do not permit free rotation 2.Physical States and Transitions: Consider a long. PE or polystyrene (PS). chaotic.  Partly crystalline polymers contain crystalline domains (crystallites) mixed with amorphous domains. regular polymer chain connected by a series of single bonds. the presence of large bulky groups inhibit rotation.g. On cooling a polymer from the melt. No rotation in an orderly solid state. the more intense the molecular motion.. e. With the potential for free rotation around single bonds. e. PS is largely amorphous 6.

Illustration of a Partly Crystalline Polymer .

Many polymers show an abrupt change in physical properties at this point. The following figure shows the changes in specific volume with temperature for an amorphous polymer not having a true melting point. . is a liquid above 100°C (the melting point. as well as for a crystalline polymer.. When cooled below Tm .The Glass Transition Temperature (Tg): Non polymeric materials have only one phase change between the solid and liquid states. Many polymeric materials have two phase changes between the solid and liquid states. is often actually a temp. ‘Tm’). the flexible solid becomes a stiff. When heated. defines a boundary between the rubbery or plastic state and the brittle. They change sharply from a liquid to a brittle Tg solid at Tm (similar to NaCl & H2O). brittle solid (a ‘glass’) at -110°C.  Tg. This occurs at the melting point (also called the freezing point).  Partly crystalline (partly amorphous) polymers have both a Tm and a Tg. sodium chloride melts (freezes) sharply at 801°C and water melts (freezes) at 0°C. glass state. 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. Tm  Completely amorphous polymers have a Tg but no Tm. For example.  Completely crystalline polymers have a Tm but no Tg. and refractive index as well as flexibility. However. melt-like arrangement. Tg is assumed to be the same for both polymers. sometimes called ‘the second-order’ transition temperature. range. and dielectric properties. specific heat. By rapidly cooling a crystalline polymer specifi amorphous from the melt.e. Note the abrupt change in density at Tg as segmental motion stops. low density polyethylene (LDPE). on further cooling. elasticity. density. i. they gradually soften and liquefy over a temperature range (similar to glass). The temperature at which the transition from a flexible (leathery) solid to a stiff. it is a flexible (leathery) solid. brittle solid (glass) is called the stiffening temperature or the ‘glass transition temperture’ (Tg). sometimes called ‘the first-order’ transition temperature.  Tm. For example.

The result is a flexible plastic used for raincoats and shower curtains. The garment’s shape is locked in place when the heat and moisture are removed leaving a wrinkle free appearance. Bulky side chains increase Tg as in PS vs. .. The moisture lowers Tg below the iron temperature allowing the removal of creases (due to polymer flow). Tg drops to ca.Plasticizers: Plasticizers are nonvolatile solvents purposely added to lower the stiffness (Tg) of a polymer. loosely packed has lower Tg than when tightly packed. The same polymer.6 (a polyamide) 267 45 Non polar polymers have low melting points.e. The familiar process of steam ironing a garment usually takes place between Tg and Tm. migration of the plasticizer occurs eventually resulting in the onset of embrittlement. 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. 160 30 polypropylene (atactic) low density ca. Polarity incrases Tm and Tg values. PE & PP. polyvinyl chloride. a stiff polymer with a high Tg (82ºC) is made flexible by the addition of up to 40% dioctylphthalate or tricresylphosphate plasticizer. Study these and be able to explain the relative differences. i. Polymer Tm (C) Tg (C) polyethylene (high density-high MW) 137 -20 polyethylene (low density-low MW) 100 -110 polypropylene (isotactic) high density ca. -80 C. For example. Many commercial fibers are plasticized by small amounts of water. The plasticizer occupies space between molecular chains and reduces intermolecular attraction acting as a lubricant. Values of Tg for some common plastics are listed. Fogging or ‘sweating’ may occur at high temperatures.

higher melting point (typically >125 C vs. and the small methylene groups fit easily into a crystal lattice. Physical properties of polyethylenes related to molecular structure. In the case of polyethylenes.91-0.. the stereochemistry of the polymer is not a variable because of the symmetry of the ethylene monomer.000 MPa C atoms PE % Amorphous 0 0.85 - - - LDPE 50-70 0.. Table II compares some of the fundamental properties of the more important commercial PE's. Its molecular structure is very simple and perfectly regular. greater stiffness and tensile strength. with frequent branching. therefore crystallizes easily and to a high degree (over 90%) even though its secondary forces are small. linear PE has higher density than the branched material (density range of 0.94-0.the length and frequency of occurrence of chain branching.9410. is thus only partially (50-70%) crystalline.92-0..94 g/cm3).925 106-112 9-15 20-40 LLDPE 65-80 0..91-0. greater hardness. Linear high density PE.  Linear PE has essentially the best structure for chain packing.  Branching impairs the regularity of the structure and makes chain packing difficult.Structure and Properties Conventional Polyethylenes: As a result of different polymerization processes for commercial PE and the versatility of these processes. 0. Many of the differences in physical properties between low-density and highdensity PE's can be attributed to the higher crystallinity of the latter. (2).965 g/cm3 vs.94 125 13-20 10-25 HDPE 80-95 0. The greater the linearity of the polymer molecule. The structural variables are twofold: (1).965 125-138 21-37 < 5-10 Polymethylene > 95 0. Branched low density PE.  Thus. 112 C). and less permeability to gases and vapors. Amorphous PE and highly crystalline polymethylene are also included to delineate the full range of properties attainable with PE. Type of Crystallinit y Density g/cm3 Melting Point C Tensile # Branches Strength per 1. with infrequent branching. the greater the tendency toward crystallization. Table II. a number of types of PE are manufactured. . each specially engineered for particular applications. 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 average molecular weight and molecular weight distribution.97 143 - unbranche d The tabled data reveals clear trends which can be understood in terms of the molecular structure of these polymers.

CHM 605 Part 4 MOLECULAR WEIGHT OF POLYMERS .

i. with the liquid viscosity increasing with the chain length. when the molecular weight exceeds a threshold value. 140 120 100 80 mp (° C) 60 40 20 0 0 500 1000 1500 DP of PE Figure 2.000.002 g/cm3) is reported as 143 C. completely unbranched polyethylenes of infinitely high molecular weight (density at 25 C of 1. C40H82 (81 C). Here crystallinity has a greater influence on the melting point. The melting point of 100% crystalline. Highly linear polyethylene of molecular weight greater than three million exhibits a melting point of 132 C. but oligomers with a DP of 3 or more (that is. .  As the DP value exceeds 400.   Note the increase in melting points with increasing molecular weight in the paraffin series: C20H42 (35 C).Molecular Weight: Because of their large molecular size. polyethylenes become hard resins with melting points above 100 °C. polymers possess unique chemical and physical properties. Melting point of PE versus degree of polymerization. C60H122 (99 C).  The dimer of ethylene (butylene) is a gas. The dependence of the melting point of polyethylene on the degree of polymerization (DP) is shown in Figure 2. C30H62 (65 C). C50H102 (92 C). and becomes more prominent as the size of the molecule increases.. These properties begin to appear when the polymer chain is of sufficient length. or the molecular weight exceeds about 10. C6 or higher paraffins) are liquids. and those with DP around 50 are waxes. and C70H142 (105 C). The increase in melting point with chain length in the higher molecular weight range is small.e. Polyethylenes with DP of about 30 are grease-like.

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

e. Recall that each of these effects are proportional to the number of moles of solute (polymer) present in a solvent. light scattering: The intensity of light scattered is proportional to the square of the mass of the particle in solution 4. Since it is not generally possible to physically segregate. average molecular weight is determined by a variety of techniques. photometer. 6. boiling point elevation. etc.g. 5. In contrast. conductance. Such compounds are said to be monodisperse. gel permeation chromatography: (size exclusion chromatography). a concentration gradient is established with larger particles in the lower layers of the solution.. titration of reactive end groups such as carboxylic acid groups or amine groups 2. vapor pressure lowering. e. and osmotic pressure. all molecules are the same size and therefore have identical molecular weights (M). freezing point depression. count and weigh all the molecules of a sample. end group analysis. . Methods of determining molecular weight include the following 1. ultracentrifuge: After centrifuging a solution of the polymer at high speeds for several weeks. each giving slightly differing values. 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.g. A suitable detector (e. colligative properties. virtually all synthetic polymers and some natural polymers are polydisperse. viscosity: Ostwalt viscometers are used to measure relative viscosity of dilute solutions of polymers.   The extent of variation of molecular weight and size in a polymer sample is known as its molecular weight distribution. i. A crosslinked porous polystyrene packing ('gel') separates polymer molecules based on their size. Thus most polymers do not contain molecules of the same size and therefore do not have a single molecular weight.. The viscosity is directly proportional to the polymer chain length. (MWD) and the MWD has considerable influence upon the physical properties of the polymer.) indicates the relative concentrations. 3. The concentration of polymer at various depths is then determined by optical methods. The molecular weight of a polymer is reported as an average.Molecular Weight Distribution of Polymers: In ordinary chemical compounds such as sucrose.

They can be titrated with standard HCl titrant.15 g/mol).Molecular Weight Determination of Polymers A non polymeric substance has a fixed molecular weight.00 mL of 0. The tests may be grouped into three types. End Group Analysis involves titrating reactive end groups with a standard acid or base titrant. 1. For example. Titration of a weighed portion of the polymer with standard NaOH yields the number average MW of the polymer.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 . In order to determine the average MW of a polymer sample we conduct chemical and/or physical tests. Calculate the number average MW of a polyester given that titration of a 10.00 g sample requires 50. This is physically impossible to do. number average MW tests. A sample of a polymer contains chains of different lengths. polyesters (made by reacting a diol with excess diacid) will have carboxylic acid end groups on all chains. If we could separate all polymer chains in a sample and count the number of chains of each weight. For example. (ans. 40. This only works for polymers that have reactive end groups. a polyamide made by reacting a diacyl chloride with excess diamine produces a polymer with amine end groups on all chains. all glucose molecules (C6H12O6) have the same molecular weight (180.0100 M NaOH titrant. Different tests may give different values for the molecular weight of the same sample. Thus a polymer does not have an exact and absolute molecular weight. weight average MW tests and viscosity average MW tests. we could then calculate an average molecular weight for a given sample. Number Average MW Tests: These tests measure the number of molecules present in a sample. Similarly.

At the same temperature. (ans. 10. These properties vary in proportion to the number of moles (mole fraction) of a substance and hold for both polymeric and non polymeric substances.46 mmHg. the number average MW can be calculated. Calculate the number average MW of a water soluble polymer given the following data. pure H2O boils at 17. the polymer solution will boil when the applied pressure becomes equal to the vapor pressure of the solution. = 1247 g/mol) . At 20°C this solution boils at 17. 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.000g polymer are dissolved in 36.2. Colligative Properties include vapor pressure lowering. Since a liquid boils when its vapor pressure equals the pressure of atmosphere above it. a) Vapor Pressure Lowering: Recall from Raoult’s law that the vapor pressure above a solution is inversely proportional to the mole fraction of non volatile solute dissolved in a solution. By accurately measuring this pressure and the pressure at which pure solvent boils (at the same temperature). boiling point elevation.53 mmHg.03 g H2O. freezing point depression and osmotic pressure.

74 °C.84 °C. The normal bp of CCl4 is 76. m = molality of solute.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).000g polymer are dissolved in 100.95 Kelvinskgsolventmolesolute-1. kb is constant for a solvent Calculate the number average MW of a polymer given that when 10. Tb = kbm where Tb = bpelevation. the solution boils at 76. = 4950 g/mol) Boiling Point Elevation of Calcium Chloride Solutions . (ans. The molal bp elevation constant for CCl4 is 4.00 g CCl4.

Freezing Point Depression of Calcium Chloride Solutions .

08206 Latmmol-1K-1.0 g/mol) dissolved in 2. The solution is prepared by dissolving 72.20 atm and 12.00 g urea (MW = 60. m = molality of solute.00 mL.14 °C. by lowering the freezing point of water). M = molarity. Tf = kfm where Tf = fpdepression. For example. The molal fp depression constant for water is 1.00 g H2O.  = MRT where  = osmotic pressure. T = Kelvins. = 1.00 L H2O at 20°C. = 298. osmotic pressure displays a large response for even dilute solutions. which must be applied to a solution to prevent osmosis. (ans.000 g/mol) . The gas constant (R) is 0.4 m H2O!) Calculate the number average MW of a water soluble polymer given that when 15. its osmotic pressure at 20°C measures 0.86 Kelvinskgsolventmolesolute-1. (Recall that NaCl and/or CaCl2 are applied to roads to melt ice.00605 atm (ans. to prevent the passage of pure solvent through a semi permeable membrane into a solution. calculate the osmotic pressure (atm and m H2O) of a solution of 6. Unlike the other colligative properties. i.c) Freezing Point Depression: The freezing point of a liquid is depressed when a non volatile solute is dissolved in it..00 g polymer in 500. 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. (ans.00 g polymer is dissolved and diluted to 200. R = gas constant. = 1910 g/mol) d) Osmotic Pressure: Osmotic pressure is that pressure.e.

3. conductance. The concentration of polymer at various depths is then determined by optical methods. A crosslinked porous. 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. like aqueous NaCl. The viscosity is directly proportional to the polymer chain length. The intensity of light scattered is proportional to the square of the mass of the particle in solution. photometer. Ostwalt viscometers are used to measure relative viscosity of dilute solutions of polymers. however. in some cases. polystyrene packing ('gel') separates polymer molecules based on their size. Viscosity Viscosity Average Molecular Weight: viscosity avg. 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. MW To use light scattering to measure MW. MW . Ultracentrifuge: After centrifuging a solution of the polymer at high speeds for several weeks. Intensity 1. weight average MW is plotted. When light passes through a solution of polymeric solutes. are larger than the wavelength of UV and. are transparent to light because the solute and solvent molecules are much smaller than the wavelength of light. To determine the viscosity average MW of a polymer. Size is proportional to weight. one needs a series of standards of equal concentration but varying and known MW. the light is scattered. weight avg. one must first prepare a series of standards of equal concentration (w/v) but varying and known MW. Polymer molecules. Gel Permeation Chromatography: (size exclusion chromatography). Light Scattering: Solutions of non polymeric solutes.) indicates the relative concentrations. 2. visible light. A calibration curve of intensity of scattered light vs. A suitable detector (e. 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.Weight Average Molecular Weight Tests: These tests measure the average size of polymer molecules. a concentration gradient is established with larger particles in the lower layers of the solution.g. The light bends around small molecules and ions and such particles are therefore invisible. etc.

Similarly. of polymer with molecular 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. DPw = 610 .000. DPn = 540. Mn  N 1M1 + N 2 M 2  N1 + N 2 N M N i   ni M i i i where … Ni = # moles polymer with molecular wt. the molecular weight of each species is multiplied by the weight fraction of that species. just as the average score in a series of organic tests is calculated by adding all scores and dividing by the number of tests. the molecular weight of each species was multiplied by the mole fraction of that species. summing these. = Mi ni = mole fraction polymer with molec.000 g/mol. Note that DP = ( M/weight of a mer) Ans: Mn = 15. = Mi wi = weight fraction of polymer with molec. wt. = Mi Weight-Average Molecular Weight: In the calculation of Mn . DPn. and then dividing this sum by the total number of molecules (or moles). is the common arithmetic mean calculated by counting the number of molecules (or moles) of each particular size.Number-Average Molecular Weight: The number-average molecular weight. and DPw. in the calculation of weight-average molecular weight. wt. Mw.000. Mw = 17. Mw . M w   wi M i W M  W i i i  N M M  NM i i i i i NM  NM i 2 i i i where … Wi = wt. Calculate Mn. Mn.

200 2-4 epoxy resins 0. 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.05 . Light scattering is dependent upon the size (weight) of particles.2.350 40 .50 2.. Polymer Mn ( 10-3) Mw ( 10-3) Mw / Mn alkyd resins 25 . Only in the case of a monodisperse.1 . Mv .4 0.7 1. Values of Mv always lie between Mw and Mn and are usually 10 to 20% below Mw .Both Mn and Mw are theoretical concepts and are not calculated in the manner of the previous example.8 polybutadiene 2 . Some typical data is given in the following table .1 .600 1..35 .   The ratio Mw / Mn .  Mn is obtained by end-group analysis and by colligative properties. is a measure of the MWD of a polymer.1. the presence of short chains acts as a plasticizer by reducing entanglement of the larger polymer chains.5 acrylic polymer 25 .52 1.50 50 . does Mw = Mn . the wider the MWD of a sample. increased toughness) and of lower melt viscosity than a sample of the same polymer with a lower index.0 .1. where all molecules are the same size. .35 . These methods measure the number of molecules in a sample.0. The example serves to illustrate the concepts. this method is commonly performed and the molecular weight determined by this method is called viscosityaverage molecular weight. The farther the polydisperse is from 1. Viscosity-Average Molecular Weight: Because viscosity measurement of a polymer solution is comparatively simple. called the polydispersity index.  Mw is obtained by light scattering techniques (photometric methods).1 A large polydispersity index indicates a polymer is more deformable (reduced stiffness. Polydispersity Index: For all polydisperse polymers Mw is always greater than Mn .

CHM 605 Part 11 POLYMER TEST QUESTIONS .

...... 13........ and 4 State 4 characteristics each for thermoplastics and thermosets... a) .............. i............. state whether it is amorphous or crystalline............... 6. is a polymer used by the Mayan Indians of S.. 16.. is known as the ‘Father of polymer chemistry’... Give names or draw structures of polymers using IUPAC and common nomenclature for all examples covered in class... pot handles d) .. a) amorphous polymer c) glassy state b) crystalline polymer d) tacticity Sketch polymer chains in their planar zigzag conformation showing .. branched and crosslinked polymer chains. Increasing the number of branches in a polymer a) causes the crystallinity to ..... a) Staudinger’s 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.... d) causes the tensile strength to .. was the polymer first used as an ivory replacement c) ........... 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.... isotactic/atactic PP........ State.... Sketch the appearance of linear..... 17.. Name 3 thermoplastics and 3 thermosets. 3....... .......... Write the 7 SPI recycle symbols and the corresponding chemical names and abbreviations. 10. 20. a) isotactic polypropylene b) syndiotactic polystyrene c) atactic poly(vinyl chloride) For each polymer in question 11.... 9. define or explain in as few words as possible .... 5...POLYMER REVIEW 1.. List 2 polymers with low Tg and 2 with high Tg State if these polymers have high or low Tg and why: PS. b) causes the density to . and PE Answer with  or ......... 3. PVC... was the first thermal resistant polymer. America b) ....... show & name 4 different arrangements of comonomers in copolymers List the 3 most important feedstock monomers for making polymers.e... 14..and trans-1.. Explain briefly..4-polybutadiene to show their stereochemistry... 12... the function of a plasticizer with respect to its physical properties.... 8...... 19.. List 9 groups of polymers classified according to end use and 1 chemical name of a polymer for each.... 21..... Sketch cis. 18. 15... 4....... c) cause the melting point to . Explain briefly .. 7..... Give one example each for monomers with functionality of 2....... 11... Polymer history: Complete the following . 2... Explain in as few words as possible .

PTFE. Then show one propagation step. 53. PE. . 45. PVC. PP. Name 2 subdivisions of step-growth polymerizations and briefly state their difference. redox initiators) 38. Include termination by combination and disproportionation.. 54. AlCl3. 35. 27. molecular weight of 200. Show the mechanism by which water can deactivate a cationic (or anionic) end group. 23. and state the names of 2 common free radical initiators for free radical polymerization. List 2 initiator accelerators (i.. 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. Arrange these 3 molecular weights in decreasing magnitude as determined on the same sample of polymer. BF3. or Li + naphthalene). 49. 47. Draw resonance structures to show how styrene can stabilize either a benzylic cation. 25. Draw structures of 3 monomers which can be polymerized a) cationically.e. List 4 non-catalytic methods and 3 catalytic methods of polymerization 32. pressure) of the high pressure PE process and the Ziegler-Natta Coordination Process. 33.2) 43. ZnCl2). Show the mechanism of their dissociation and give the formula/structure of their products. 50. Give the approximate density and melting point of LDPE and HDPE.1 vs. 34. What are the cause. List examples of 4 different types of polymers that are polymerized by the step-growth method. Give the formulas or structures of. SnCl4. Show the mechanism of initiation of anionic polymerization of vinyl chloride with methyl lithium (or with Li metal.g. 24. a) adding chain transfer agent b) adding a very small quantity of initiator 36. and chain transfer agent.22. Give the name and structure of 2 free radical inhibitors. List the approximate conditions (temp. 46. 42. or viscosity-average molecular weight. PS) (Instructor’s choice on a test). ‘propagation at the tip’? Which process causes each of these kinds of propagation? 52. Write equations to show cationic polymerization of isobutylene including its initiation with H2SO4 or with a Lewis acid catalyst (e.. Calculate the average MW of a polymer using data re: any of the colligative properties as discussed in class 28. Using a simple graph (with labeled axes) explain the difference between a polydispersity index of 1. By means of equations show the complete cycle of free radical polymerization of a vinyl polymer (e. 40. List 3 dienes which can be free-radical polymerized and draw their structures. What is the catalyst commonly used in the Ziegler-Natta process? 51. chain transfer with solvent (e. Name the 3 main types of polymerization and name 1 example of a polymer for each. 4. Why are they needed? 39. anion or free radical (Instructor’s choice on test). effect and mode of prevention of the Tromsdorff-Norish Effect? 41. State the effect avg.g. Show the mechanism by which functional end groups can be created by termination with carbon dioxide and with ethylene oxide.g.4 or 1. 30. Show the mechanism of initiation and propagation of free radical polymerization of a diene (1. State the type of polymer produced by each and list 2 applications for both types of PE. CCl4). What effect does a high polydispersity index have on a polymer’s physical properties? 31. molecular weight on. What is meant by ‘propagation from the root’ vs.000 26. polymer.. List 6 methods of determining average molecular weight of a polymer and state whether the method determines number-average. weight-average. Show the mechanism of step-growth polymerization of poly(ethylene terephthalate) (or Nylon 6). b) anioinically 44. 48... Give the formula and name of 1 chain transfer agent. 37. 29. Use resonance structures to show and explain why one of these inhibitors is effective..

..... c) ........... 62. and name one polymer that demonstrates this.... and disadvantages of bulk polymerization and 3 polymers commonly produced by this technique. 77.................. 66................ calculate DP and the contour length of chain extended molecules of PE with an average MW of 750... Given that the planar zigzag conformation of extended chain PE has a contour length of 2... etc..... force is applied to a polymer specimen that is 1/8” thick” and ½” wide.... Name 2 polymers whose maximum use temperature is close to 300 C.... List 5 inert fillers and 3 reasons for adding them.... 60................ final length at 9........ Given various stress strain curves........ 64....... 78. 68.. Name 2 plasticizers..... load is 2.... List 1 toughness modifier............ label the following points......... Suspension and Emulsion polymerization... 57......... an industrial method of stress induced crystallization... Name 3 high performance resins and the physical properties that set them apart...... advantages. State 2 important changes that occur during stress-induced crystallization to increase stiffness and strength............. 80... 74............ 61)..... Calculate the stress (in SI and British units) when 2. Give the name of the following ............. the name for localized reduction of cross sectional area of a thermoplastic under tensile loading.... Calculate (to 3 sig figs) the proportional and % strain of a specimen with an original length of 3... Show the polymerization of HMDI and HMDA (one step) and name the type of polymer formed. crystals which form during quiescent crystallization from the melt.. 82........55 Angstroms... Name 2 colorant additives...... 65......... proportional strain.........00165 in........... 83............. Sketch the main components of a melt spinning unit and label its parts...... thermal stabilizers...55.. 75....... thickness = ¼” and original length of 2.. Briefly state the meaning of a ‘failure test’ and list 6 examples...6 and PET (see Table V on p. UV absorbers... and proportional limit... the units which hold polymer crystals together. Briefly explain how polymer hardness is measured... Give the maximum use temperature of Nylon-6. elastic limit.. Give the maximum use temperature of LDPE and HDPE ........... 58. a) ......00 103 lb.... Elongation under long-term loading is called ....... soft and tough. the maximum draw ratio for HDPE f) . 69...002 in.000 in.... b) .. 67... tensile strength.. classify the polymer as soft and weak......... State briefly why solution crystallized polymer crystals are brittle.... and a final length of 3. List 5 reinforcing additives..... 63.. Draw and name the polymer produced from -caprolactam 59....... 81....... 84......... List the ingredients.... 76...... Given a series of stress strain curves. Report in SI units to 3 sig figs............ 61............ d) ......... and toughness for the linear initial stress strain data from a tensile test given the following data ......20  103 lb....... Name the ultimate property that the ‘notched Izod test’ measures.. yield strength.. 73..000 in. 79. Name one of each of the following stabilizers... 72............. ultimate strength..5”.... Repeat the previous question for Solution.... 70..... original specimen width = 0........ stress..000..4-diisocyanotobenzene and 1... Show the mechanism by which ethylene oxide is polymerized. the maximum draw ratio for polyesters and polyamides e) .2-diaminoethane. Draw & name the reagents & product of polymerization of 1.. Name 3 engineering resins and 3 specific applications for such resins... antioxidants.. 71. 56. rupture strength..... Calculate the modulus of compressive elasticity..................................

. a) highest s. 6-6. i. direct esterification. symbols. nylon 6 resin.. 92. amine + carboxylic acid.. show the polymerization of nylon 6-6 from 2 different sets of starting reagents.. Write the names.g. specific applications of PC 95.. List 4 different.85. 98. 88. Also show the byproduct formed. PC resin. value) b) highest Tm (& give approx. (& give approx. 5. show the formation of PET by any of the four polymerization methods. List 4 different. ester exchange. 89. 6-12. Using equations. amine + acid anhydride. Write the formulas and names of the monomers and formulas of the polymers for the following polyamides. 100. Write equations to show the polymerization reaction that forms. 91. Write the chemical formulas and names of CTFE. 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 . FEP. Write equations to show the polymerization reaction that forms poly(dimethylsiloxane) or poly(diphenylsiloxane) (Instructor’s choice on test). specific applications of PET 94. specific applications of aliphatic nylons and 4 specific applications of Aramid fibers.. Kevlar and Nomex 87. and PTFE resin and choose the 1 which best fits each of the following descriptions. using an acid chloride. ring opening of a lactam 86.. 6.e. specific applications of silicones. Show the byproduct (condensation product) formed. nylon 2. or using an acid anhydride (Instructor’s choice on test). 12. List 4 different. Draw the mechanism for the synthesis of a polyamide by reaction of: an amine + acid chloride. Write the complete mechanism of acid catalyzed Fischer esterification. 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. and numbers of the 7 recycle groups for plastics as per the Society for Plastics Industry (SPI). value) l) highest crystallinity (& give approx. 4.. 96. By means of an equation. value) m) lowest crystallinity c) lowest Tg (& give approx. 97. 90. and PVF2 polymers. specific applications of PTFE 99. List 4 different. Compare silicone elastomer. Write the mechanism of esterification from acid chloride or acid anhydride (Instructor’s choice on test).

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