edited by

GEORGE B. KAUFFMAN
California State University. Fresna
FreSnO. CA 93740

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
by blacksoil on the flood plains of the Nile. The Arabs added
the prefixel to form the wordalchemy, which became known
as "Ewotian black art". The oractitioners of alchemv soent
cent$& in their search for t<e "philosopher's stone9<dhich
-
would he capable of chaneine-. plebeian substances.' such as
lead, into more desirable ones, such as gold ( I ) .
In spite of their efforts during many man-years, the alche-
mists failed to accomplish their objectives. This failure was
due in Dart to secrecy and lack of essential laboratorv. a..
ma-
ratus.any historians 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-
vestigations, 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 resoonsihle for the develonment of
our petrochemical industry: I t is of interest to note that,
simultaneouslv with Woh.ler's svnthesis of an oreanic com-
pound, urea, in the absence of a'kital force,"in 1828,Dumas
became so impressed with ethylene (HzC=CHz) that he
called it a 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 he called alkenes, hut the term ole-
fins also continue to be used almost universally to describe
these important organic compounds.
The first large-scale use of alkenes was for the production
of isopropyl alcohol in 1920 (3).This compound is sometimes
incorrectly called isopropanol instead of 2-hydroxypropane
(H3CCH(OH)CHd. 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
carhon-containing compounds changed from less than 2%
from ethylene in 1925, to over 98% from this and other
alkenes, such as propylene (l-propene) in 1987. The annual
production of ethylene and propylene in the United States
in 1987 was 17.5 million tonsand 9.2 million tons, rwpective-
IY(4).
In addition to ethylene and propylene, there are several
other important alkenes, such as l-hutene (HzC=CHCHz-
CHd, isohutylene (HzC=CH(CH&), l-hexene (HzC=CH-
(CH2)&H3)and l-octene (H2C=CH(CHz)&H3). One of the
principal uses for these alkenes is for the production of
thermoplastics, such as low-density polyethylene (LDPE),
high-density polyethylene (HDPE), linear low-densitypoly-
ethylene (LDPE), high-density polyethylene (HDPE), lin-
ear low-density polyethylene (LLDPE), hutyl rubber, and
copolymers of ethylene and propylene (EP) (5).
There are two principal types of plastics, viz., thermosets
and thermoplastics. The thermosets, such as the phenolic
resins (Bakelite) are three-dimensional network polymers
that cannot he 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 he reversibly soft-
ened by heat.
With the exception of cross-linked polyethylene, which is
cross-linked by exposure to high-energy radiation, most of
the polymers of alkenes are thermoplastics. LDPE is a high-
ly amorphous (noncrystalline), transparent polymer that is
produced by the addition of organic peroxides, such as ben-
zoyl peroxide (CsH5COOOOCCsH~), which is cleaved to pro-
duce free radicals (CsH5CO0.),which serve as initiators for
the propagation, i.e., the sequential 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 hv the a~olicationof heat. This
rapid production process, in khich HDPE or other thermo-
plastics are softened hv the a ~ ~ l i c a t i o
ofnheat oressure and
allowed to cool to a soiid in amold cavity, is cailed injection
molding. Simulated structures for LDPE and HDPE are
shown below:

670 Journal of Chemical Education


LLDPE is a linear copolymer of ethylene and a higher
molecular weight alkene, such as l-butene, l-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 CROUP
Butyl rubber, which has excellent resistance to perme-
ation by gases, is a copolymer of isobutylene (98%) and
isoprene (2% CHF=C(CH~)CH=CH~).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-
tedfor reasons of simplicity. Thiselastomer, which isused 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 perspiration, underwear made from P P fi-
hers was used bv skiers in the 1988 Winter Olvm~ics.. . The
pendant methyliroups in commercial P P are all on the same
- - -
side of the chain. This hirhlv cwstalline .oolvmer
" is called
isotactic P P (it PP).
In contrast to the rieid solid i t PP. random co~olvmersof
ethylene and propylene (EP) are nonrigid, e~adomericsol-
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-
uea brasiliensis), which are cultivated in Indonesia, Malay-
sia, and 1.iberia. Very little NR is obtained from Brazil, but
from a standpoint of self-sufficiency it is important to note
that the amount of NH obtained frum guayule (Parthenium
argentalum) continues to increase. The guayule plant,
which isa member of the sunflower familv. is beinr cultivat-
ed in northern Mexico and the southwes~'unitedU~tates. It
contains 10%NH and can be harvested mechanically.
Most of the derivatives of alkenes, such as isopropyl alco-
hol, ethanol, polyethylene, polypropylene, poly(viny1 chlo-
ride), and polystyrene are substituted alkanes (-H2C-C-
HX) (9),but elastomers such as natural ruhber (NR), zutta-
percha, and many synthetic rubbersaresubstituted alkenes.
Gutta-percha (Paloqurum oblongifoliurn) and balata
(Miniso~snlobo~o)have the same chemical formula as NR.
but, as shown by the following skeletal formula, these ard
plastics or trans-polyisoprene, while NR is a cis-polyiso-
prene.
NR (cis-polyisoprene) gutta-percha, balata
(trans-polyisoprene)
~-
Whiie NR was used for centuries for the waterproofing
clothine and for makine tlachtli rubber balls. it was too
~~ ~
&icky to merit extensive commercialization. charles Mac-
Kintosh nrovided a nhvsical solution to this nroblem bv
making a' ruhber s&d&ch between two sheets of c o t t i
cloth. However. the real "breakthroueh" was made bv
Charles ~ o o d y e kwho, cross-linked N R heating
~ ~ it with*
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 ruhber was an alkene. Good-
year heated NR with a large amount of sulfur and obtained
hard rubber
~~ ~-~~ (ebonite).
The first s;ntheticelastomer (rubber) was also an alkene.
which could be vulcanized bv heatine with sulfur. This elas-
~ ~
tomer was produced by ~ a k h e w A s d Strange in England
( l l ) , and by Harries in Germany in 1911 (12), and later by
Kondakov in Russia. These investigations used metallic so-
dium as an initiator for the polymerization of 2,3-dimethyl-
butadiene (H2C=C(CH3)C(CH3)=CHz). More than 2500
tons of both soft and hard rubber was produced by the
vulcanization of this "methyl rubber" by the Germans dur-
inp World War I. However, since "methyl rubber" tires were
n(z reinforced by carbon black, they were not tough enough
to be used on tanksand military trucks. Hence this synthetic
rubber had limited use durine World War 1.
The first American syntheiic rubber was a polyethylene
sulfide, called Thiokol. 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 viuylacetyleue (HC=C-CH=CHd to chloroprene
(H&CICH=CH2) and produced a substituted alkene
elastomer called Dupreue. Duprene, which is now called
Neoprene, is a heat- and oil-resistant elastomer, which is not
used for making tires, but is used for gaskets, hose, and other
mechanical goods (13).
Tschunkur, Bock, and Konrad, who were employed as
research chemists by I. G. Farbenindustrie, produced more
useful elastomeric copolymers of butadiene (HzC=CH-
CH%H2) and styrene (HzC=CH(CsHs)) or acrylonitrile
(H&-CH(CN)). These elastomers, which were called Buna
Sand 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 was produced in the United
States in 1987.
The production of synthetic cis-polybutadiene and cis-
polyisoprene by the butyllithium (C4H9Li) or titanium tri-
chloride-diethylaluminum chloride (TiCIa-(C2H&4ICI)-
initiated polymerization of butadiene or isoprene could be
called the ultimate fulfillment of the alchemists' dreams.
These vulcanized products, which are alkene derivatives, are
Volume 66 Number 8 August 1989 671
similar to NR. Over 410,000 tons of polyhutadiene elastomer Since the histow of polvmeric hvdrocarhons is essentidv
was produced in the United States in 1987. the same as that oi the alkanes (9i and alkenes, predictions
of chemical properties are not difficult. I.ikewise, their syn-
Conclusions thesis hy the p&lymerizationof alkenes and dienes, respec-
No gold was ever produced hv the transmutation of base tively, simplifies commercial production.
metalshy the alchemists. ow ever,
as shown by the follow- The alchemist would he impressed to learn that the world-
ing table, many millions of tons of useful products have been wide production of gold in 1987 was about 3.5 million
produced by the conversion of alkenes to more useful prod- pounds. Yet he would he disappointed to learn that no gold
ucts. Many of these, such as thepolydienes, consist of alkene was made by transmutation.
repeating units in their polymer chains. The production of Perhaps he would he more imoressed to learn that 53.7
alkenes and alkene derivatives in millions of tons in the billion pbunds of plastics was pro;fuced in the United States
United States in 1987 is shown below (4,15): in 1987 by chemists and chemical engineers who transmuted
crude petroleum into essential products. Of course, this use-
Ethylene ful transmutation, which made the alchemists' dream come
FTopylene true, was predicted in the 19th Psalm, which states "more to
Ethylene dlchloride
Vinyl chloride
he desired are they [alkanes and alkenes] than gold".
Styrene
Ethylene oxide
Propylene oxide Literature CRed
lsopropyl alcohol 1. Leicpster H. M. Histarieol&rekgmund of Chemistry. Wiley: N m York. 1966
2. Moore F. J.: Hall, W.T.Hktorrof Chemistry; Mffiraw-Hill: New York, 1918.
HOPE 3. Austin, G. T. Shrem'r ChemirnlPlaeera Industries; MeGraacHill: New York, 1984.
PP 4. Reiaeh, M. C. Chem. Eng. Neum 1988,66(15),30.
LOPE 5. Seymour.R.6 . ; Cheng,T.,M. HucoryofPalyo1ofim;Reidel:Dordreehf TheNaber-
LLDPE lands, 1986.
6. Seymour, R 6.; Camah.., C. E Polymer Chemistry. An Intmductian: Dekker: New
styrene polymers
Vinyl chloride polymers
SBR
Polybutadiene
EP, E W M 1 1 \latlhra$. P.E :Slrsoje, E.H. Dnl. Pal. 24.790119101
NBR I2 Herr;cr C.1.S.Pat L.ISR.u5T,!l4lDI
Neoprene 19. N,,llu~aw A . r . t u t ~ .W' S . I I M ~ ~ ~ P:C-.A.S
.E. J . A ~ . c ~ ~ ~1 .~ sx 1o. ~
5.4197
Butyl rubber 14. T%hddkur.E.;B~uck,W.U.S. Pat.1,938,731(1933).
NR 15. Martho, R. J. Modem Ploalica 1988,W11.95.

672 Journal of Chemical Education