product, of
ch miltry
Alkenes and Their Derivatives
The Alchemists' Dream Come True
Raymond B. Seymour
Department of Polymer Science, University of Southern Mississippi, Southern Station Box 10076, Hattiesburg, MS 39406
The words alchemy and chemistry were derived from
che mia, which was also the name for Egypt, which was
blessed byblack soil on the flood plains of the Nile. The
Arabs added the prefix el to form the word alchemy,which
became known as "Egyptian black art". The practitioners of
alchemy spent centuries in their search for the
"philosopher's stone", which would be capable of changing
plebeian substances, such as lead, into more desirable ones,
such as gold (1).
Inspite of their efforts during many man-years, the alche
mists failed to accomplish their objectives. This failure was
due in part to secrecy and lack of essential laboratory appa
ratus. Many historian s have written many volumes on
alche mists and their accomplishments, but too little has
been written about modern chemists and the results of their
in vestigat ions, which have been primarily responsible for
to day's high standard of living and well-being.
Among the many products of modern chemistry are the
alkenes, which have been responsible for the development
of our petrochemical ind ust ry. It is of interest to note that,
simultaneously with Wohler's synthesis of an organic com
pound, urea, in the absence of a " vital force," in1828,
Dumas became so impressed with ethylene (H2C= CH2)
that he
called ita base that, if soluble in water, would turn litmus
blue (2).
Four Dutch chemists produced an oily derivative by the
addition of chlorine to ethylene and hence called it olefiant
(oil-forming) gas. IUPAC has recommended that these un
saturated hydrocarbons be called alkenes, but the term ole
fins also continue to be used almost universally to describe
these important organic compounds.
The first large-scaleuse of alkenes was for the production
ofisopropyl alcohol in 1920 (3 ). This compound is
sometimes incorrectly called isopropanol instead of 2-
hydroxypropane
(H3CCH(OH)CH3). Almost 600,000 tons of isopropyl
alco hol is produced annually in the United States.
Ethylene soon became the preferred building block for
many other organic compounds. Thus the source of these
carbon-containing compounds changed from less than 2%
from ethylene in 1925, to over 98% from this and other
alkenes, such as propylene (1-propene) in 1987. The annual
production of ethy lene and propylene in the United States
in 1987 was 17.5million tons and 9.2 million tons, respective
ly (4).
In addition to ethylene and propylene, there are severa!
other important alkenes, such as 1-butene (H2C = CH CH2 -
CH3), isobutylene (H2C=CH(CH3}i), 1-hexene (H2C = CH
(CH2h CH 3) and 1-octene (H2C= CH(CH2)sCH3). One ofthe
edited by
GEORGE B. K AUFFMAN
California State University, Fresno
Fresno, CA 93740
principal uses for these alkenes is for the product ion of
thermoplastics , such as low-density polyethylene (LDPE),
high-density polyethylene (HDPE), linear low-density poly
ethylene (LDPE), high-density polyethylene (HDP E), lin
ear low-density polyethylene (LLDPE), butyl rubber, and
copolymers of ethy lene and propylene (EP) (5).
There are two principal types of plast ics, viz., thermo
sets and thermoplastics. The thermosets, such as the
phenolic resins (Bakelite) are three-dimensional network
polymers that cannot be dissolved by solvents or softened,
without decomposition, by heat. The thermoplastics,such as
LDPE, which is used by the dry cleaners as a film for
protecting solvent-cleaned clothing, are large, linear
molecules, which are soluble in selected solvents and can be
reversibly soft ened by heat.
With the exception of cross-linked polyet hylene, which is
cross-linked by exposure to high-energy radiation , most of
the polymers of alkenes are thermoplast ics. LDPE is a
high ly amorphous (noncrystalline), transparent polymer
that is produced by the addition of organic peroxides, such
as ben zoyl peroxide (C5HsCOOOOCC5H 5) , which is
cleaved to pro duce free radicals (C6H5COO·),which serve
as initiator s for the propagation, i.e., the sequent ial
addition of ethylene molecules to the free radicals formed
by the addition of the initiator to the ethylene monomer.
HDPE has fewer branches on its polymer chain and thus
has a higher volume than LDPE. This linear polymer is
molded into useful articles by the application of hea t. This
rapid production process, in which HDPE or other thermo
plast ics are softened by the application of heat pressure and
allowed to cool to a solid in a mold cavity, is called inject ion
molding. Simulated structures for LDPE and HDPE are
shown below:
LOPE
(higher vol ume. - l o v e r d e ne i t y )
670 Journal of Chemical Education

HOPE
< low&r volume-higher de n.s i ty >
LLDPE is a linear copolymer of ethylene and a higher
molecular weight alkene, such as 1-butene, 1-hexene, or 1-
octene. Both monomers or building blocks are present, as
repeating units, in the copolymer chain. As shown in the
simulated figure below, LLDPE consists of a linear chain
with ethyl, butyl, or hexyl groups on its polymer chain.
These pendant groups cause an increase in volume, and
hence the density of LLDPE is lower than that of HDPE (6,
7).
PENDANT GROUP
r•
LLDPE
Butyl rubber, which has excellent resistance to perme
ation by gases, is a copolymer of isobutylene (98%) and
iso prene (2% CH 2= C(CH3 )CH = CH2). An isoprene
mole cule contains two double bonds, but only one double
bond is
present in the isoprene repeating units of the copolymer.
Two hundred thousand tons of butyl rubber are produced
annually in the United States. Unlike HDPE or LDPE,
butyl rubber is an alkene, as shown in the following
simulat ed skeletal formula, in which the hydrogen atoms
are omit ted for reasons of simplicity. This elastomer, which
is used as an inner tube in tires, was invented by Sparks
and Thomas in 1937 (8).
Because of the presence of methyl pendant groups, poly
propylene (PP) has a lower density than HDPE. Since it
does not absorb perspirat ion, underwear made from PP fi
bers was used by skiers in the 1988 Winter Olympics. The
pendant methyl groups in commercial PP are all on the
same side of the chain. This highly crystalline polymer is
called isotactic PP (it PP).
In contrast to the rigid solid it PP, random copolymers of
ethylene and propylene (EP) are nonrigid, elastomeric sol
ids. When a diene is one of the reactants, the product of
polymerization is unsaturated, and EPDM can be cross
linked by sulfur.
Natural rubber is obtained by tapping rubber trees (He
vea brasiliensis), which are cultivated in Indonesia, Malay
sia, and Liberia. Very little NR is obtained from Brazil, but
from a standpoint of self -su fficiency it is important to note
that theamount of NR obtained from guayule (Parthenium
argentatum) continues to increase. The guayule plant,
which is a member of the sunflower family, is being
cultivat ed in northern Mexico and the southwest United
States. It contains 10% NR and can be harvested
mechanically.
Most of the derivative s of alkenes, such as isopropyl alco
hol, ethanol, polyethylene, polypropylene, poly(vinyl chlo
ride), and polystyrene are substituted alkanes (- H2 C - C -
HX) (9), but elastomers such as natural rubber (NR), gutta
percha, and many synthetic rubbers are substituted alkenes.
Gutta-percha (Palaquium oblongifolium) and balata
(Minisops globosa) have the same chemical formula as NR,
but, as shown by the following skeletal formula, these are
plastics or tra ns-polyisoprene, while NR is a cis-polyiso
prene.
c e e+
1 1 1
C=C C=C
+
1 1 1
+e
NR (cis-polyisoprene) gutta-percha, balata
+
(trans-polyisoprene)
While NR was used for centuries for the waterproofing
clothing and for making tlachtli rubber halls, it was too
sticky to merit extensive commercialization. Charles Mac
Kintosh provided a physical solution to this problem by
making a rubber sandwich between two sheets of cotton
cloth. However, the real "breakthrough" was made by
Charles Goodyear, who cross-linked NR by heating it with
a small amount of sulfur in 1838 (10).
Since only one repeating isoprene unit in 100 units in the
polymer chain was joined to another chain by the sulfur
cross-link, this vulcanized soft rubber was an alkene. Good
year heated NR with a large amount of sulfur and obtained
hard rubber (ebonite).
The first synthetic elastomer (rubber) was also an alkene,
which could be vulcanized by heating with sulfur. This elas
tomer was produced by Matthews and Strange in England
(11), and by Harries in Germany in 1911 (12), and later by
Kondakov in Russia. These invest igations used metallic so
dium asan initiator for the polymerization of 2,3-dímethyl
butadiene (H2C= C(CH3)C(CH 3)= CH,2) More than 2500
tons of both soft and hard rubber was produced by the
vulcanization of thís "methyl rubber" by the Germans dur
íng World War l . However, since " methyl rubber" tires
were not reinforced by carbon black, they were not tough
enough to be used on tanks and military trncks. Hence thís
synthetíc rubber had limited use during World War l.
The first American synthetíc rubber was a polyethylene
sulfíde, called Thíokol. This elastomer possessed the unique
elastic properties of rubber but was not an alkene. However,
in 1931, Carothers and Collins of Du Pont converted explo
sive vinylacetylene (HC= C- CH= CH2 ) to
chloroprene (H2-CCICH=CH2) and produced a subst itut ed
alkene elastomer called Duprene. Duprene, which is now
called Neoprene, is a heat- and oil-resistant elastomer,
which is not used for making tir es, but is used for gaskets,
hose, and other mechanical goods (13).
Tschunkur, Bock, and Konrad, who were employed as
research chemists by l. G. Farbenindustrie, produced more
useful elastomeric copolymers of butadiene (H2C= CH
CH=CH2) and styrene (H2C= CH (CsH5)) or acrylonitrile
(H2C= CH (CN)).These elastomers, which were called Buna
S and Buna N, respectively, were introduced in Germany in
the late 1920's (14).
These elastomeric copolymers, which are now called SBR
and NBR, respectively, contain alkene repeating units in
their polymer chains. They are used as alternatives to NR.
Almost 950,000 tons of SBR wa§,-produced in the United
States in 1987.
The production of synthet ic cis-polybutadiene and cis
polyisoprene by the butyllithium (C4H 9Li ) or titanium tri
chloride-d iethylaluminum chloride (1'iCla- (C2H 5h A1Cl)
initiated polymerization of butadíene or isoprene could be
called the ultimate fulfíllment of the alchemists' dreams.
These vulcanized product s, Vl'.hich are alkene derivatives,
are
Volume 66 Number 8 August 1989 671
 similar to NR. Over 410,000 tons ofpolybutadiene elastomer Since the history of polymeric hydrocarbons is essentially
was produced in the United States in 1987. the same as that of the alkanes .(9) and alkenes, predictions
Concluslons of chemica l properties are not difficult. Likewise, their syn
thesis by the polymerization of alkenes and dienes, respec
No gold was ever produced by the transmutat ion of base tively, simplifies commercial production.
metals by the alchemists. However, as shown by the follow The alchemist would be impressed to learn that the world
ing table, many millions of tons of useful products have wide production of gold in 1987 was about 3.5 million
been produced by the conversion of al kenes to more useful pounds. Yet he would be disappointed to learn that nogold
prod ucts. Many of these, such as the polydienes, consist of was made by transmuta tion.
alkene repeating units in their polymer chains. The Perhaps he would be more impressed to learn that 53.7
production of alkenes and alkene derivatives in millions of billion pounds of plast ics was produced in the United
tons in the United State s in 1987 is shown below (4, 15): States in 1987 by chemists and chemical engineers who
Ethylene 17.5 transmuted crude petroleum into essential products. Of
Propylene 9.25 course, t his use ful transmutation, which made the
Ethylene dichloride 6.9 alchemists' dream come true, was predicted in the 19th
Vinyl chloride 4.1 Psalm, which sta tes "more to be desired are they [alkanes
Styrene 4.0 and alkenes] than gold".
Ethylene oxide 2.8
Propylene oxide 1.3
lsopropyl alcohol 0.6 Llterature Clted
HOPE 4.0 l. Leicester H. M. Historical Background o/ Chemistry; Wiley: New York, 1956.
pp 3.3 2. Moore F. J.; Hall, W. T. History o/ Chemist ry; McGraw- Hill: New York, 1918.
LDPE 2.7 3. Aus tin , G. T. Shreve•s Chemical Process Industries;McGraw- Hill: New York, 1984.
LLDPE 1.5 4. Reisch, M. C. Chem. Eng. News 1988,66(15), 30.
5. Seymour, R. B.; Cheng,T., Ed. History o/ Polyolefins; R e idel: Dordrecht, The Nether
Styrene polymers 3.0 lands, 1986.
Vinyl chloride polymers 4.5 6. . Sey mour, R. B.; Carraher, C. E. Polymer Chemist ry: An Introductio n; Dek ker: Ne w
SBR 0.93 Yo,rk 1988.
7. McMillan, F. M. T he Chain St raighteners; MacMillan: London, 1979.
Polybutadiene 0.41 8. Morron, M. In History o/ Polymer Science and Technology;Dekke r: New York, 1982.
EP, EPDM 0.28 9. Seymour, R. B. J. Chem. Educ.1989,
NBR 0.07 66,59. 10. Goodyear, C. U.$. Pat.. 3633 (1844).
11. Matth ews, F. E.; Stra nge, E. H. Brit . Pa t. 24,790 (1910).
Neoprene 0.13
12. Harr ies, C. U.S. Pa t. 1,058,056 (1913).
Butyl rubber 0.2 13. Nieuwland , J. A.; Calcott, W. S.; Downing, E. P.; Carter, A.S. J. Am. Chem.
NR 0.75 Soc.1931,
53, 4197.
14. Tschunkur, E.; Buc k, W. U.$. Pat. 1,938,731(1933).
15. Martino, R.J. Mod ern Plastics 1988, 65(1), 95.
672 Journal of Chemical Education