Chapter 10

Chemicals from Propylene and Butylene

As we learned in Chapter 8, the official production of propylene is

usually about half that of ethylene, only because a large part of the propylene
is used by petroleum refineries internally to alkylate gasolines. This captive
use is not reported. Of the propylene used for chemical manufacture, nearly
40% is polymerized to polypropylene, to be discussed in a later chapter. Of
the remaining amount of propylene, seven chemicals from the top 50 are
manufactured.
These are listed in Table 10.1.
Their industrial
manufacturing methods are summarized in Fig. 10.1. Note that four of these
chemicals, cumene, phenol, acetone, and bisphenol A, are also derived from
a second basic organic chemical, benzene.

1.

ACRYLONITRILE (2-PROPENONITRILE)
CH2=CH-C=N
Table 10.1 Propylene Derivatives in the Top 50
Acrylonitrile
Propylene Oxide
Cumene
Phenol
Acetone
Bisphenol A
ft-Butyraldehyde

propylene

acrylonitrile

propylene oxide
styrene

cumene

acetone

phenol

bisphenol A

fl-butyraldehyde

isobutyraldehyde

Figure 10.1 Synthesis of propylene derivatives in the top 50 chemicals.

Acrylonitrile and other three-carbon analogs containing a double bond

have a common name derived from the word acrid, meaning strong and
disagreeable, in regard to the odor of most of these chemicals. Compounds
in this family are given here with their common names.
acrylonitrile
acrylic acid

acrolein
acrylamide
Acrylonitrile was made completely from acetylene in 1960 by reaction
with hydrogen cyanide. For some years ethylene oxide was the raw material
for addition of HCN and elimination of H2O.

Neither of these methods is used today. Around 1970 the industry

switched from C2 raw materials and classical organic chemical addition
reactions to the ammoxidation of propylene. Now all acrylonitrile is made
by this procedure, which involves reaction of propylene, ammonia, and
oxygen at 400-45O0C and 0.5-2 atm in a fluidized bed Bi2O3^nMoO3
catalyst. The yield is approximately 70%.
2CH2=CH-CH3 + 2NH3 + 3O2

** 2CH2=CH-C=N + 6H2O

The mechanism is undoubtedly a free radical reaction that occurs very

easily at the allyl site in propylene, forming the resonance-stabilized allyl
radical.
CH2=CH-(^H2 **

** ^H2-CH=CH2

By-products of this reaction are acetonitrile, CH3-C=N, and hydrogen

cyanide. This is now a major source of these two materials. Interestingly,
the C2 by-product acetonitrile has a bp of 81.60C, whereas acrylonitrile with
three carbons has a lower bp of 77.3 0C, quite an unusual reversal of this
physical property's dependence on molecular weight. The TWA of
acrylonitrile is 2 ppm and it is on the list of "Reasonably Anticipated to Be
Human Carcinogens."
Table 10.2 outlines the uses of acrylonitrile. One important use of
acrylonitrile is in the polymerization to polyacrylonitrile. This substance and
its copolymers make good synthetic fibers for the textile industry. Acrylic is
the fourth largest produced synthetic fiber behind polyester, nylon, and

Table 10.2 Uses of Acrylonitrile

Adiponitrile
33%
Acrylic fibers
25
ABS/SA resins
23
Acrylamide
9
Nitrile elastomers
3
Miscellaneous
7
Source: Chemical Profiles

polyolefm. It is known primarily for its warmth, similar to the natural and
more expensive fiber wool. Approximately 23% of the acrylonitrile is made
into plastics, including the copolymer of styrene-acrylonitrile (SA) and the
terpolymer of acrylonitrile, butadiene, and styrene (ABS). Acrylamide has a
fast-growing use as a flocculent for water treatment units. Exports of
acrylonitrile are over 1 billion Ib/yr.
The largest use of acrylonitrile is the manufacture of adiponitrile, made
by two different methods. One method is by the electrohydrodimerization of
acrylonitrile. It is converted into hexamethylenediamine (HMDA), which is
used to make nylon. The other adiponitrile synthesis is C4 chemistry, which
will be discussed later in this chapter, Section 8.
2CH2=CH-C=N -^-+ N=C-(CH2)4-C=N ^ H2N-(CH2)6-NH2
2e'
acrylonitrile
adiponitrile
HMDA

About one third of all adiponitrile is made from acrylonitrile. In the

electrodimerization of acrylonitrile a two-phase system is used containing a
phase transfer catalyst tetrabutylammonium tosylate [(W-Bu)4N+OTs"]. The
head-to-head dimerization may be visualized to occur in the following
manner.

The by-product of acrylonitrile manufacture, HCN, has its primary use in

the manufacture of methyl methacrylate by reaction with acetone. This is
covered later in this chapter, Section 4.

2.

PROPYLENE OXIDE (1,2-EPOXYPROPANE)

There are two important methods for the manufacture of propylene oxide,
each accounting for one half the total amount produced. The older method
involves chlorohydrin formation from the reaction of propylene with
chlorine water. Before 1969 this was the exclusive method. Unlike the
analogous procedure for making ethylene oxide from ethylene, which now is
obsolete, this method for propylene oxide is still economically competitive.
Many old ethylene oxide plants have been converted to propylene oxide
synthesis.

The mechanism in the first step involves an attack of the electrophilic

chlorine on the double bond of propylene to form a chloronium ion, which is
attacked by a hydroxide ion to complete the first reaction. The dilute

chlorohydrin solution is mixed with a 10% slurry of lime to form the oxide,
which is purified by distillation, bp 340C. The yield is 90%. Propylene
oxide has a TWA of 20 ppm and is on the list of "Reasonably Anticipated to
Be Human Carcinogens."
A new variation of the chlorohydrin process uses /-butyl hypochlorite as
chlorinating agent. The waste brine solution can be converted back to
chlorine and caustic by a special electrolytic cell to avoid the waste of
chlorine.
The second manufacturing method for propylene oxide is via
peroxidation of propylene, called the Halcon process after the company that
invented it. Oxygen is first used to oxidize isobutane to /-butyl
hydroperoxide (BHP) over a molybdenum naphthenate catalyst at 9O0C and
450 psi. This oxidation occurs at the preferred tertiary carbon because a
tertiary alkyl radical intermediate can be formed easily.
Reaction:

BHP
Mechanism:

(1)
(2)
(3)

The BHP is then used to oxidize propylene to the oxide. This reaction is
ionic and its mechanism follows. The yield of propylene oxide from
propylene is 90%.
Reaction:

Mechanism:

The /-butyl alcohol can be used to increase the octane of unleaded

gasoline or it can be made into methyl /-butyl ether (MTBE) for the same
application. The alcohol can also be dehydrated to isobutylene, which in
turn is used in alkylation to give highly branched dimers for addition to
straight-run gasoline.
Since approximately 2.2 Ib of/-butyl alcohol would be produced per 1 Ib
of propylene oxide, an alternative reactant in this method is ethylbenzene
hydroperoxide. This eventually forms phenylmethylcarbinol along with the
propylene oxide. The alcohol is dehydrated to styrene. This chemistry was
covered in Chapter 9, Section 6 as one of the syntheses of styrene. Thus the
side product can be varied depending on the demand for substances such as
/-butyl alcohol or styrene. Research is being done on a direct oxidation of
propylene with oxygen, analogous to that used in the manufacture of
ethylene oxide from ethylene and oxygen (Chapter 9, Section 7). But the
proper catalyst and conditions have not yet been found. The methyl group is
very sensitive to oxidation conditions.
As an aside to the manufacture of propylene oxide via the chlorohydrin
process let us mention use of this type of chemistry to make epichlorohydrin.

allyl chloride

epichlorohydrin

Table 10.3 Uses of Propylene Oxide

Polypropylene glycol
60%
Propylene glycol
25
Glycol ethers
4
Miscellaneous
11
Source: Chemical Profiles

Although not in the top 50, it is an important monomer for making epoxy
adhesives as well as glycerine (HO-CH2-CHOH-CH2-OH). Propylene is
first chlorinated free radically at the allyl position at 50O 0 C to give ally 1
chloride, which undergoes chlorohydrin chemistry as discussed previously to
give epichlorohydrin. The student should review the mechanism of allyl free
radical substitution from a basic organic chemistry course and also work out
the mechanism for this example of a chlorohydrin reaction.
Table 10.3 summarizes the uses of propylene oxide. Propylene glycol is
made by hydrolysis of propylene oxide. The student should develop the
mechanism for this reaction, which is similar to the ethylene oxide to
ethylene glycol conversion (Chapter 9, Section 8). Propylene glycol is a
monomer in the manufacture of unsaturated polyester resins, which are used
for boat and automobile bodies, bowling balls, and playground equipment.
But an even larger use of the oxide is its polymerization to
poly(propylene glycol), which is actually a polyether, although it has

poly (propylene glycol)

propylene glycol

propylene oxide
n = 7-35

a polyurethane

hydroxy end groups. These hydroxy groups are reacted with an isocyanate
such as toluene diisocyanate (TDI) to form the urethane linkages in the high
molecular weight polyurethanes, useful especially as foams for automobile
seats, furniture, bedding, and carpets. Poly(propylene glycol) is used to
make both flexible and rigid polyurethane in a 90:10 market ratio.

3.

CUMENE (ISOPROPYLBENZENE)

Cumene is an important intermediate in the manufacture of phenol and

acetone. The feed materials are benzene and propylene. This is a FriedelCrafts alkylation reaction catalyzed by solid phosphoric acid at 175-2250C
and 400-600 psi. The yield is 97% based on benzene and 92% on propylene.
Excess benzene stops the reaction at the monoalkylated stage and prevents
the polymerization of propylene. The benzene:propylene ratio is 8-10:1.

(excess)

Interestingly, if benzene is left out similar conditions are used to

manufacture the trimer and tetramer of propylene. The cumene is separated
by distillation, bp 1530C.
The mechanism of the reaction involves electrophilic attack of the
catalyst on the double bond of propylene to form the more stable secondary
cation, which reacts with the TI cloud of benzene to give a delocalized ion.
Deprotonation rearomatizes the ring.

A major industry shift to zeolite-based catalyst systems is expected to

lower production costs and improve product yield.
Approximately 95% of the cumene is used to make phenol and acetone.
A small amount is used to make a-methylstyrene by dehydrogenation. This
material is used in small amounts during the polymerization of styrene to
vary the properties of the resulting copolymer.

catalyst

4.

ACETONE (2-PROPANONE)

Presently there are two processes that make acetone in large quantities.
The feedstock for these is either isopropyl alcohol or cumene. In the last few
years there has been a steady trend away from isopropyl alcohol and toward
cumene, but isopropyl alcohol should continue as a precursor since
manufacture of acetone from only cumene would require a balancing of the
market with the co-product phenol from this process.
This is not always easy to do, so an alternate acetone source is required.
In fact, isopropyl alcohol may become attractive again since cumene can be
used to increase octane ratings in unleaded gasoline, and phenol, as a
plywood adhesive, has its ups and downs with the housing industry. The
percentage distribution of the two methods is given in Table 10.4.
In the minor route isopropyl alcohol, obtained from the hydrolysis of
propylene, is converted into acetone by either dehydrogenation (preferred) or
air oxidation. These are catalytic processes at 50O0C and 40-50 psi. The
acetone is purified by distillation, bp 560C. The conversion per pass is 7085% and the yield is over 90%.
Table 10.4 Manufacture of Acetone
Year
1959
1975
1985
1999

From Isopropyl Alcohol

80%
46
15
6

From Cumene
20%
54
85
94

dehydrogenation

air oxidation

The main route, the formation of phenol and acetone from cumene
hydroperoxide, involves a fascinating rearrangement of cumene
hydroperoxide where a phenyl group migrates from carbon to an electrondeficient oxygen atom. This was discovered by German chemists Hock and
Lang in 1944 and commercialized in 1953 in the U.S. and U.K. The
hydroperoxide is made by reaction of cumene with oxygen at 110-1150C
until 20-25% of the hydroperoxide is formed. The oxidation step is similar
to that of cyclohexane to cyclohexane hydroperoxide and will be treated in
Chapter 11, Section 4. Students should be able to work out this mechanism
on their own with this help! Concentration of the hydroperoxide to 80% is
followed by the acid-catalyzed rearrangement at 70-8O0C. The overall yield
is 90-92%.

phenol
cumene

cumene hydroperoxide

acetone

Side products are acetophenone, 2-phenylpropan-2-ol, and amethylstyrene. Acetone is distilled first at bp 560C. Vacuum distillation

acetophenone

2-phenylpropan-2-ol

oc-methylstyrene

recovers the unreacted cumene and yields a-methylstyrene, which can be

hydrogenated back to cumene and recycled. Further distillation separates

phenol, bp 1810C, and acetophenone, bp 2020C. The weight ratio of

acetone:phenol is 0.6:1.0.
The mechanism of the rearrangement is an excellent practical industrial
example of a broad type of rearrangement, one occurring with an electrondeficient oxygen. The mechanism is given in Fig. 10.2.

a protonated hydroperoxide

simultaneous

cumene hydroperoxide

resonance stabilized

a hemiketal

acetone

phenol
resonance stabilized

Figure 10.2 Mechanism of the cumene hydroperoxide rearrangement.

Table 10.5 Uses of Acetone

Acetone cyanohydrin
45%
Bisphenol A
20
Solvent
17
Aldol chemicals
8
Miscellaneous
10
Source: Chemical Profiles

Table 10.5 gives the uses of acetone. A very important organic chemical
that just missed the top 50 list, methyl methacrylate, is made from acetone,
methanol, and hydrogen cyanide. Approximately 1.2 billion Ib of this
compound is manufactured and then polymerized to poly(methyl
methacrylate), an important plastic known for its clarity and used as a glass
substitute. The synthesis is outlined as follows.

methyl methacrylate

The first reaction is a nucleophilic addition of HCN to a ketone, the

second is a dehydration of an alcohol and hydrolysis of a nitrile, and the
third is esterification by methanol.
Aldol chemicals refer to a variety of substances desired from acetone
involving an aldol condensation in a portion of their synthesis. The most
important of these chemicals is methyl isobutyl ketone (MIBK), a common
solvent for many coatings, pesticides, adhesives, and pharmaceuticals.
Approximately 0.17 billion Ib of MIBK were made in recent years. The
synthesis is outlined on the next page.

diacetone alcohol

mesityl oxide

MIBK

Diacetone alcohol is a solvent used in hydraulic fluids and printing inks.

Recall that the aldol condensation is an example of a variety of carbanion
reactions used to make large molecules from smaller ones. An aldehyde or a
ketone with at least one hydrogen on the carbon next to the carbonyl will
react to give the aldol condensation. The mechanism is given as follows.

5.

BISPHENOL A (BPA)

Bisphenol A is manufactured by a reaction between phenol and acetone,

the two products from the cumene hydroperoxide rearrangement. The
temperature of the reaction is maintained at 5O 0 C for about 8-12 hr. A slurry

of BPA is formed, which is neutralized and distilled to remove excess

phenol. Some o,p isomer is formed along with the predominance of p,p
isomer.

bisphenol A

The student should develop the mechanism of this reaction using the
following stepwise information: (1) protonation of the carbonyl; (2)
electrophilic attack on the aromatic ring; (3) rearomatization by proton loss;
(4) another protonation, but then loss of a water molecule; and (5)
electrophilic attack and rearomatization.
The major uses of BPA are in the production of polycarbonate resins
(63%) and epoxy resins (27%). Polycarbonates have major outlets in
automotive parts, compact discs, eyeglasses, and sheet and glazing
applications, and have caused bisphenol A consumption to more than double
during the past decade. Epoxy resins are two-component adhesives for very
strong bonding. Miscellaneous uses include flame retardants (mostly
tetrabromobisphenol A) and other polymer manufacture. Polycarbonate
grade bisphenol A is >99% p,p isomer. The epoxy grade is 95% p,p. The
p,p and o,p isomers can be separated by a combination of distillation and
crystallization.

6.

H-BUTYRALDEHYDE (BUTANAL)

Butyraldehyde is made from propylene by the oxo process, also known as

hydroformylation. Synthesis gas (CO + H2) is catalytically reacted with
propylene to the butyraldehydes. The approximate yields are 67% nbutyraldehyde and 15% isobutyraldehyde.

H-butyraldehyde

isobutyraldehyde

The classic oxo catalyst is octacarbonyldicobalt at 130-1750C and 250

atm. This reacts with hydrogen to give hydridotetracarbonyl cobalt, the
active catalyst in the oxo process.

The mechanism of carbonylation/hydrogenation involves addition of the

alkene to form a TI complex, followed by alternating additions of H, CO, and
H.

Newer catalysts are being studied to increase the ratio of w-butyraldehyde

to isobutyraldehyde.
The main use of w-butyraldehyde is the production of n-butyl alcohol by
hydrogenation. w-Butyl alcohol is used for ester synthesis, especially butyl
acetate, aery late, and methacrylate, common solvents for coatings.

butyl acetate

butyl acrylate

butyl methacrylate

7.

CHEMICALS FROM THE C4 FRACTION

Chemicals obtained from petroleum having four carbons are

manufactured at a considerably lower scale than ethylene or propylene
derivatives. Only five C4 compoundsbutadiene, acetic acid, vinyl acetate,
isobutylene, and methyl /-butyl ether (MTBE)appear in the top 50. The
manufacture of butadiene and isobutylene, as well as the separation of other
C4 compounds from petroleum, is described in Chapter 8, Sections 3-5.
Acetic acid was discussed as a derivative of ethylene in Chapter 9, Section 3
and is discussed as a derivative of methane in Chapter 12, Section 3. Vinyl
acetate was discussed in Chapter 9, Section 4. A few important derivatives
ofC 4 chemistry will be briefly mentioned here as well as MTBE.

8.

BUTADIENE DERIVATIVES

Besides butadiene, another important monomer for the synthetic

elastomer industry is chloroprene, which is polymerized to the chemically
resistant poly chloroprene. It is made by chlorination of butadiene follow by
dehydrochlorination. As with most conjugated dienes, addition occurs either
1,2 or 1,4 because the intermediate allyl carbocation is delocalized. The 1,4isomer can be isomerized to the 1,2-isomer by heating with cuprous chloride.
Reaction:

15%NaOH
-HCl
10O0C

chloroprene
Intermediate:

Another derivative of butadiene, hexamethylenediamine (HMDA), is

used in the synthesis of nylon. We have already met this compound earlier
in this chapter since it is made from acrylonitrile through adiponitrile.

Approximately two thirds of all adiponitrile is made from 1,3-butadiene and

2 moles of hydrogen cyanide. This is an involved process chemically and it
is summarized in Fig. 10.3. Butadiene first adds one mole of HCN at 6O 0 C
with a nickel catalyst via both 1,2- and 1,4-addition to give respectively 2methyl-3-butenonitrile (2M3BN) and 3-pentenonitrile (3PN) in a 1:2 ratio.
The 1,2-addition is the usual Markovnikov addition with a secondary
carbocation intermediate being preferred. Fig. 10.4 shows an ADN reactor.
Next isomerization of the 2M3BN to 3PN takes place at 15O0C. Then more
HCN, more catalyst, and a triphenylboron promoter react with 3PN to form
5% methylglutaronitrile (MGN) and mostly adiponitrile (ADN). The ADN is
formed from 3PN probably through isomerization of 3PN to 4-pentenonitrile
and then anti-Markovnikov addition of HCN to it. The nickel catalyst must
play a role in this last unusual mode of addition, and a steric effect may also
be operating to make CN" attack at the primary carbon rather than a
cationically preferred secondary carbon. A complicated set of extractions
and distillations is necessary to obtain pure ADN.
Even then the
hexamethylenediamine (HMDA) made by hydrogenation of ADN must also
be distilled through seven columns to purify it before polymerization to
nylon. Fig. 10.5 pictures some HMDA distillation units.

ADN

HMDA

Figure 10.3 Manufacture of adiponitrile and hexamethylenediamine from 1,3-butadiene.

Figure 10.4 Reactors used in the conversion of 1,3-butadiene and HCN to adiponitrile.
(Courtesy of Du Pont)

Figure 10.5 Distillation columns associated with the purification of hexamethylenediamine. (Courtesy of Du Pont)

9.

METHYL /-BUTYL ETHER (MTBE)

In 1984 methyl /-butyl ether (MTBE) broke into the top 50 for the first
time with a meteoric rise in production from 0.8 billion Ib in 1983 to 1.47
billion Ib in 1984 to be ranked 47th. In 1990 it was 24th with production over
6 billion Ib, and in 1995 it was 12th at 18 billion Ib. A full discussion of the
current economic status of MTBE is given in Chapter 7, Section 4 as the
important gasoline octane enhancer. That is its only major use. MTBE is
manufactured by the acid catalyzed electrophilic addition of methanol to
isobutylene.

or ion
exchange
catalyst

MTBE

10.

OTHER C4 DERIVATIVES

An important antioxidant for many products is butylated hydroxytoluene

(BHT), more properly named 4-methyl-2,6-di-/-butylphenol. Acid-catalyzed
electrophilic aromatic substitution of a /-butyl cation at the activated
positions ortho to the hydroxy group of/?-cresol yields this product, pCresol is obtained from coal tar or petroleum.

BHT

For many years maleic anhydride (MA) was made from benzene by
oxidation and loss of two moles of CO2. Even as late as 1978 83% of maleic

anhydride was made from benzene. However, the new Occupational Safety
and Health Administration (OSHA) standards for benzene plants required
modifications in this process, and butane is also cheaper than benzene. As a
result since 1989 all maleic anhydride is now made from butane. This has
been a very rapid and complete switch in manufacturing method.

The mechanism is not well understood, but the intermediates in the

process are butadiene and furan. The uses of maleic anhydride are

furan
summarized in Table 10.6. Unsaturated polyester resins are its prime use
area. Food acidulants include fumaric and malic acids. Malic acid competes
with citric acid as an acidulant for soft drinks, and it is added to products that
contain aspartame, the artificial sweetener, because it makes aspartame taste
more like sugar. Agricultural chemicals made from MA include daminozide
(Alar), a growth regulator for apples which in 1989 was found to be
carcinogenic because of a breakdown product, unsymmetrical
dimethylhydrazine (UMDH). Alar is needed to keep the apple on the tree,
to make a more perfectly shaped, redder, firmer apple, and to maintain
firmness in stored apples by reducing ethylene production.
Table 10.6 Uses of Maleic Anhydride
Unsaturated polyester resins
Lube oil additive
Copolymers
Agricultural chemicals
Fumaric acid
Malic acid
Miscellaneous
Source: Chemical Profiles

62%
11
7
4
3
3
10

fumaric acid

daminoazide (Alar*)

malic acid

UDMH

The oxo process is used to convert the 4 fraction to C5 derivatives.

Synthesis gas is catalytically reacted with 1-butene to give pentanal which
can be hydrogenated to 1-pentanol (w-amyl alcohol), giving a route to C5
compounds in larger amounts than what would be available from C5 alkanes
in petroleum.

catalyst

Suggested Readings
Chemical Profiles in Chemical Marketing Reporter, 7-29-96, 12-2-96, 3-2098, 7-13-98, 1-4-99, 3-22-99, 4-5-99, 12-27-99, and 5-8-00.
Kent, Riegel's Handbook of Industrial Chemistry, pp. 830-846.
Szmant, Organic Building Blocks of the Chemical Industry, pp. 265-378.
Wiseman, Petrochemicals, pp. 65-88.
Writeoff and Reuben, Industrial Organic Chemicals, pp. 149-224.