Chapter 18

Elastomers

1.

HISTORY AND ECONOMICS

Although naturally occurring rubber from the tropical tree has been
known for ages, the Spanish navigator and historian Gonzalo Valdez (14781557) was the first to describe the rubber balls used by Indians. Natural
rubber was brought back to Europe from the Amazon in 1735 by Charles
Condamine, a French mathematical geographer, but it remained only a
curiosity. Michael Faraday made a rubber hose from it in 1824. But it was
not until Charles Goodyear discovered vulcanization in 1839 that natural
rubber got its first wave of interest. As the story goes, Charles became so
involved with his job that he set up a laboratory at home to study the
chemistry of rubber. Because his wife hated the odor of his experiments, he
could only continue his work at home when she was not around. While
studying the effect of sulfur and other additives on the properties of rubber
he was interrupted unexpectedly by his wife one day when she returned
home early from shopping. He quickly shoved his latest mixture into the
oven to hide it. As fate had it, the oven was lit, the rubber was vulcanized,
and the modern era of elastomer research was born. His first patent covering
this process was issued in 1844.
Today both natural rubber, an agricultural crop, and synthetic elastomers
are multi-billion dollar businesses. Looking back at Fig. 16.1, we see that
Synthetic Rubber (NAICS 325212) totals $5.7 billion. It is a large area of
polymer use and is 1% of Chemical Manufacturing. But in the related
industry covering final end products called Plastics and Rubber Products

Table 18.1 U.S. Production of Synthetic Elastomers,

Consumption of Natural Rubber
Natural rubber
29%
SBR
25
Polybutadiene
17
Ethylene-propylene
10
Nitrile
3
Polychloroprene
2
Miscellaneous
14
Source: Chemical and Engineering
News, and Chemical Economics
Handbook

Manufacturing (NAICS 326), Rubber Products (NAICS 3262) totals $35.3

billion, of which Tires (NAICS 32621) makes up $15.4 billion, showing the
dominance of the automobile tire market in this sector of the chemical
industry. The top polymer production summary in Table 1.16 gives a
numerical list of important synthetic elastomers. Styrene-butadiene rubber
(SBR) dominates the list at 1.93 billion Ib for U.S. production. All other
synthetic elastomers are much smaller. While elastomers had a slight
increase in production from 1980-1990, only 0.5% annually, SBR was down
2.3% per year. From 1990-2000 it was up 1.0% per year. The fastest
growing elastomer is ethylene-propylene, up 5.2% annually for 1990-2000.
Table 18.1 gives a breakdown in percent production of synthetic elastomers
and consumption of natural rubber in the U.S.

2.

NATURAL RUBBER

Natural rubber can be found as a colloidal emulsion in a white, milky

fluid called latex and is widely distributed in the plant kingdom. The Indians
called it "wood tears." It was not until 1770 that Joseph Priestly suggested
the word rubber for the substance, since by rubbing on paper it could be
used to erase pencil marks, instead of the previously used bread crumbs. At
one time 98% of the world's natural rubber came from a tree, Hevea
brasiliensis, native to the Amazon Basin of Brazil which grows to the height
of 120 ft. Today most natural rubber is produced on plantations in Malaysia,
Indonesia, Singapore, Thailand, and Sri Lanka. Other rubber-bearing plants

can be cultivated, especially from a guayule shrub, which is now more

important than the tree.

3.

VULCANIZATION

The process that makes the chemistry, properties, and applications of

elastomers so different from other polymers is cross-linking with sulfur,
commonly called vulcanization. The modern method of cross-linking
elastomers involves using a mixture of sulfur and some vulcanization
accelerator. Those derived from benzothiazole account for a large part of the
market today. Temperatures of 100-16O0C are typical.

SH

2-mercaptobenzothiazole

Zinc oxide and certain fatty acids (RCOOH) are also added. Although
this mechanism is by no means completely understood, it is proposed that
the benzothiazole and zinc oxide give a zinc mercaptide, and this forms a
soluble complex with the fatty acid.

Reaction of this with Sg molecules gives a persulfidic complex (X =

benzothiazole).

Interchange with the original complex leads to the formation of a mixture

of polysulfidic complexes, which are considered to be the active sulfurating
species.

These complexes then react with the allyl carbons of rubber, the most
reactive sites in the polymer.

The cross-linking occurs by reactions of the following type, where

Usually a mono- or disulfide cross-link occurs but larger numbers of

sulfur atoms are possible. If the total percentage of sulfur in the material is
<5%, it is usually very elastic. If >5% of sulfur is added, it produces a very
hard, dark, nonelastic material called ebonite, sometimes used for things like
combs and buttons.

4.

ACCELERATORS

In 1906 Oenslager and Marks at Diamond Rubber Co. (later B. F.

Goodrich Co.) began working on accelerators for cross-linking with sulfur.
These substances not only increase the rate of vulcanization but create a final
product that is more stable and less susceptible to aging. Benzothiazoles
now own 22% of the accelerator market, which is about 100 million Ib/yr.
Other types of accelerators are sulfenamides (50%), dithiocarbamates (5%),
thiurams (4%), and others (19%). The reason for the differences is that some
cause very fast vulcanization rates like sulfenamides, and some slower like
benzothiazoles. Sulfenamides such as N-cyclohexyl-2-benzothiazolsulfenamide can be made from benzothiazoles by reaction of an amine and an
oxidizing agent such as NaOCl, HNO2, or H2O2.

5.

REINFORCING AGENTS

Even with vulcanization, however, many elastomers lack the balance of

properties required for good wear. Reinforcing agents have been studied to
strengthen the rubber mechanically. In 1912 the Diamond Rubber Co. found
that addition of carbon to rubber tires caused them to last ten times longer
than without this reinforcing agent. Rubber became the substance of choice
for automobile tires and conveyor belts. Glass, nylon, polyester, and steel
now aid carbon in reinforcement for many applications. Up to 20% of these
reinforcing agents can increase the tensile strength of the rubber by 40%.

6.

ANTIDEGRADANTS

Most polymers are attacked by oxygen, ozone, and ultraviolet light.

Rubber is one such polymer that is rapidly degraded in molecular weight and
mechanical strength. Over 100 chemicals, collectively called age resistors or
age antidegradants, are added to elastomers to keep them from becoming
brittle, turning sticky, developing cracks, etc.
Most oxidation inhibitors today are either amines, phenols, or phosphites.
Phenols were suggested as early as 1870 to combat aging. Amines are now
used more than phenols in elastomers. Combinations are often used for heat,

oxygen, ozone, UV, and moisture resistance. Two examples of amine age
resistors are given here. The market is about 150 million Ib/yr, of which
amines are about 60%. The market breakdown for antidegradants is
phenylenediamines (50%), phenolics (13%), phosphites (13%), quinolines
(10%), diphenylamines (6%), and others (8%).

Other kinds of rubber chemicals are blowing agents, peptizers, and

retarders. The total market for all chemical additives for rubber is over 250
million Ib/yr.

7.

DEVELOPMENT OF SYNTHETIC RUBBER

Until the 1930s natural rubber from Hevea brasiliensis was the only
available elastomer. The United States had to, and still does, import every
pound. Although research on synthetic substitutes began before 1940 in this
country, World War II influenced speedy development of substitutes when
our supply of natural rubber from the Far East was cut off. Gasoline had to
be rationed not because of its shortage, but because of the automobile tire
shortage.
In 1910 scientists concluded that natural rubber was c/s-l,4-polyisoprene.

In 1931 Du Pont introduced the first synthetic elastomer, polychloroprene

(Neoprene, Duprene), and Thiokol Corporation introduced a polysulfide
rubber called Thiokol.
Polychloroprene, although very expensive
compared to polyisoprene, has superior age resistance and chemical
inertness. It is also nonflammable.
The Government Rubber Reserve Company in the 1940s pioneered the
development of styrene-butadiene copolymers, by far the largest volume of
synthetic rubber used today. Now usually known as SBR, it has also been
called Buna-S, 5wtadiene with a sodium (Nd) catalyst and copolymerized

with styrene, or GR-S, Government Rubber tyrene. Although it took many

years to develop, it is now the rubber of choice for most applications today,
especially automobile tires.
Polyisobutylene, commonly called butyl, was first developed in 1937 by
Esso Research and Engineering Co. Its main repeating unit is isobutylene
but it contains some isoprene for cross-linking. Originally butyl was used
for automobile tire inner tubes, where it was replaced in 1955 by tubeless
tires. However, most inner tubes still employed today are butyl rubber. In
addition to being used for engine mounts and suspension bumpers, it has
found large volume uses as liners in reservoirs and in irrigation projects.
Hypalon" chlorosulfonated polyethylene was introduced by Du Pont in
1952. Although not a high volume rubber it has found use in coatings and
hoses.

8.

CATALYSTS AND MECHANISMS

The mid-1950s saw the first commercial production by Goodrich,

Firestone, and Goodyear of polymers with stereochemistry which is
consistent or regular. In the early 1950s Karl Ziegler in Germany and Giulio
Natta in Italy found catalysts that polymerized olefins with regular
configurations. The Ziegler-Natta catalysts were primarily a combination of
a transition metal salt (TiCIs or TiCU) and an organometallic compound
(EtsAl). By proper manipulation of the ratio of these two substances either
cw-1,4- or trans-l,4-po\yisoprene from isoprene can now be prepared. The
mechanism of Ziegler-Natta polymerization was given for polypropylene in
Chapter 14, Section 2.4. Review this and work through the mechanism with
an elastomer monomer such as butadiene.
Many of the synthetic elastomers now made are still polymerized by a
free radical mechanism. Polychloroprene, polybutadiene, polyisoprene, and
styrene-butadiene copolymer are made this way. Initiation by peroxides is
common. Many propagation steps create high molecular weight products.
Review the mechanism of free radical polymerization of dienes given in
Chapter 14, Section 2.2.
Butyl rubber, polyisobutylene, is an example of cationic polymerization
with an acid. Review Chapter 14, Section 2.3. A small amount of isoprene
is added to enable cross-linking during vulcanization through the allylic
sites.

The more complex structure of this polymer must therefore be

9.

SBR VS. NATURAL RUBBER

By far the largest selling elastomers are SBR and natural rubber. SBR at
1.93 billion Ib/yr accounts for about 35% of the U.S. synthetic rubber market
and 25% of the total rubber market. The U.S. imports about 2.2 billion Ib of
natural rubber per year. A distant third is polybutadiene at 1.33 billion Ib. In
1940 natural rubber had 99.6% of the U.S. market. Today it has only 29%.
In 1950 synthetic elastomer consumption passed natural rubber use in the
U.S. Since then it has been a battle between the leading synthetic, SBR, and
the natural product. It is apparent that these two polymers are very
important. Table 18.2 summarizes and compares them by their properties.

Table 18.2 SBR and Natural Rubber

Property
Tensile, strength, psi
Percent elongation
300-400% modulus, psi
Temperature range for use, 0 C
Degree of elasticity
Tear resistance
Abrasion resistance
Age resistance
Solvent resistance
Gas impermeability
Uniformity
Versatility
Processibility
Tolerance for oil and carbon additives
Price stability
Percent of U.S. market

Natural
4,500
600
2,500
-60 to 100
Excellent
Good
Moderate
Poor
Poor
Good
Variable
Lower
Easier
Lower
Bad
29

SBR
3,800
550
2,500
-55 to 100
Good
Moderate
Good
Moderate
Poor
Moderate
Constant
Higher
Harder
Higher
Good
25

Billions of Pounds

Natural Rubber Consumption

SBR Production

Year
Figure 18.1 U.S. consumption of natural rubber vs. SBR production.
Chemical and Engineering News and Chemical Economic Handbook)

(Source:

The balance between natural rubber and SBR is a delicate one. Natural
rubber has made a comeback and reversed its downward trend.
Developments of rubber farming have raised the yield from 500 Ib/acre/yr to
2,000-3,000. Petrochemical shortages and price increases have hurt SBR.
Finally, the trend toward radial-ply tires, which contain a higher proportion
of natural rubber, favors this comeback. Fig 18.1 shows the U.S. natural
rubber consumption trends vs. U.S. SBR production, where this
"bounceback" of the natural rubber market is very evident from 1980 to the
present. The competitive price structure for these two elastomers through
the years has been very evident, and their prices are never too far apart.

10.

TIRES

No discussion of elastomers is complete without a mention of tire

technology. About 70% of all synthetic elastomers in the U.S. are used in
tires. About 264 million tires are produced in the U.S. annually, 217 million
for cars and the rest for trucks and busses. A typical tire is made up of four
parts: (1) the tread, which grips the road; (2) the sidewall, which protects the

Tread

Carcass

Liner
Sidewall

Figure 18.2 Parts of a typical tire. (Source: Wittcoff and Reuben, Industrial Organic
Chemicals in Perspective. Part Two: Technology, Formulation, and Use, John Wiley &
Sons, 1980. Reprinted by permission of John Wiley & Sons, Inc.)

sides of the tire; (3) the liner, which prevents air loss; and (4) the carcass,
which holds the layers together (Fig. 18.2).
The tire is about 50% rubber by weight. Carbon black (as a reinforcing
agent), extender oil, and the tire cord in the carcass make up the rest. The
cord was rayon for many years. Glass fiber has also been popular. But now
nylon, polyester, and steel are the major cord components. Steel became
most popular in radial tires of the 1980s and is growing in importance as the
primary reinforcing agent. About 75% of car radial tires and 92% of truck
radials are steel belted.
The tread must have the best possible "grip" to the road. Grip is
inversely related to elasticity, and natural rubber has good elasticity but poor
grip, so no natural rubber is used in automobile tire treads. Treads are
blended of SBR and polybutadiene in an approximate ratio of 3:1. Truck tire
treads do have natural rubber, between 65-100%, to avoid heat buildup and
because grip is not so necessary in heavy trucks. Aircraft tires consist of
100% natural rubber.
The carcass requires better flexing properties than the tread and is a blend
of natural rubber and SBR, but at least 60% of natural rubber. The sidewalls
have a lower percentage of natural rubber, from 0-50%. The liner is made of
butyl rubber because of its extreme impermeability to air.
The most important single trend in the U.S. tire market is the switch from
cross-ply and belted bias-ply to radial-ply tires. Radials held only 8% of the

Cross-ply

Belted bias-ply

Radial

Figure 18.3 Types of plies in tires. (Source: Writeoff and Reuben, Industrial Organic
Chemicals in Perspective. Part Two: Technology, Formulation, and Use, John Wiley &
Sons, 1980. Reprinted by permission of John Wiley & Sons, Inc.)

U.S. car tire market in 1972, but by 1977 it had grown to 50% and it is now
89%. The difference in the three is shown in Fig. 18.3.
A tire carcass contains plies of rubberized fabric. In the cross-ply the
cords cross the tire at an angle. In the belted bias-ply the cords cross at an
angle and an additional belt of fabric is placed between the plies and the
tread. In the radial-ply the cords run straight across the tire and an extra belt
of fabric is included. Radial tires have better tread wear average (66,000
miles radial, 40,000 miles bias-ply) and better road-holding ability.
However, they are more easily damaged on the sidewall and they give a less
comfortable ride. They also require a higher proportion (80% vs. 50%) of
the more expensive natural rubber. It seems likely that the popularity of
radial-ply tires will continue, and natural rubber consumption may continue
its comeback.
Today the elastomer can be reclaimed from discarded tires. Over 2
billion are available for recycling. Most reclaiming of the elastomer is done
by an alkali process with 5-8% caustic soda and heating. Reclaiming is not
profitable unless it costs no more than half as much as pure elastomer, since
reclaimed material contains only 50% elastomer hydrocarbon.
Approximately 0.66 billion Ib of elastomer is reclaimed each year in the
U.S., only about 10% of the total elastomers used. Efforts are also being
made to burn discarded tires for fuel to generate electricity, since each tire
contains energy equivalent to 2.5 gallons of oil as fuel, enough to heat an
average house for a day.

11.

IMPORTANT ELASTOMERS

We will finish this chapter with the following sections that give many of
the details for elastomers including chemical structure, manufacturing
process, some properties, and main uses. Some familiarity with these
elastomers is essential.

11.1

1.

2.
3.
4.

11.2

1.

Natural Rubber, NR, cjs-l,4-Polyisoprene

Manufacture
Biological polymerization in rubber tree
See Fig. 15.1 for biosynthesis
98% cis configuration, MW = 350,000-500,000
Properties, see table 18.2
Uses
76% in tires, other miscellaneous uses
Economics
Radial tires, favoring natural rubber, gave good growth since 1980.
Will slow now that radial tires no longer increasing
No production in U.S.
U.S. consumption from imports at 2.2 billion Ib/yr

Styrene-Butadiene Rubber, SBR5 Buna-S, GR-S

Manufacture
Introduced in 1933
Emulsion and solution polymerization
Free radical catalyst at low temperatures
75% Butadiene by weight, 85% butadiene molar

2.
3.
4.

11.3

1.

2.

3.

4.

1,2- and 1,4-Butadiene units mixed

Properties, see Table 18.2
Uses
Tires and tire products, including tread rubber, 77%; mechanical
goods, 15%; automotive, 5%; miscellaneous, 3%
Economics
2000 Production at 1.93 billion Ib
SBR suffering since 1980
Change to radial tires, favoring natural rubber, now complete
Replacement automotive parts a growing use
1990-2000 Annual change of 1.0%

Polybutadiene, BR

Manufacture
Introduced in 1955
Solution and emulsion polymerization
Ziegler-Natta catalysis
Mostly cis configuration
Properties
Excellent abrasion resistance
Low temperature flexibility
Poor traction
Uses
Tires and treads for automobiles, trucks, and buses, 72%; highimpact resin modification, 25%; industrial products (conveyor
belts, hoses, seals, and gaskets) and other applications, 3%
Economics
2000 Production at 1.33 billion Ib
Tire use expanding
Impact modifier for styrene growing

11.4

Ethylene-Propylene, EPDM, EPM, EP

1.

Manufacture
Introduced in 1963
Ziegler-Natta catalysis
EP is abbreviation, EPM means ethylene and propylene only, EPDM
means ethylene, propylene, and dimer
Most, about 85%, of EP is EPDM
55% Ethylene, 40% propylene, 5% dimer for cross-linking

2.

Properties
Low-temperature flexibility
Good age, heat, and abrasion resistance
Uses
Automotive, 44%; roofing membrane, 18%; oil additive, 10%; wire
and cable, 8%; miscellaneous, 20%
Economics
2000 Production 0.76 billion Ib
1990-2000 Increase 5.2%/yr
Fastest growing elastomer
Growing markets in automotive, building materials, and petroleum
additives

3.
4.

11.5

1.

Butyl Rubber, Polyisobutylene

Manufacture
Introduced in 1937
Low-temperature solution polymerization

2.

3.

11.6

1.

2.

3.

11.7

1.

2.

Cationic initiation
0.6-3.5% Isoprene added for cross-linking
Properties
Low permeability to air and water
Weather resistance
Noise and vibration resistance
Uses
Tires, tubes, and other pneumatic products, 83%; automotive
mechanical goods, 6%; adhesives, caulks, and sealants, 6%;
pharmaceutical uses, 4%; miscellaneous, 1%

Nitrile Rubber, Poly(butadiene-aciylonitrile), NBR

Manufacture
Introduced in 1937
Emulsion polymerization
Free radical catalyst
10-40% Acrylonitrile
Properties
Solvent, fat, and oil resistance
Wide temperature performance
Low coefficient of friction
Uses
Hose, belting, and cable, 28%; O-rings and seals, 20%; latex, 15%;
molded and extruded products, 15%; adhesives and sealants,
10%; sponge, 5%; footwear, 2%; miscellaneous, 5%

Polychloroprene, CR

Manufacture
Introduced in 1931
Emulsion polymerization
Free radical catalysis
Mostly trans configuration
Properties

Figure 18.4 Research size equipment for ply building in tires to test the usefulness of
various fibers as the plies in tires. (Courtesy of Du Pont)

3.

Flame, solvent, age, and heat resistance

Uses
Mechanical rubber goods, 30%; automotive, 30%; adhesives, 20%;
construction, 5%; coated fabrics, 5%; miscellaneous, including
wire and cable, 10%

Suggested Readings
Chemical Profiles in Chemical Marketing Reporter, 10-28-96, 11-8-99, 228-00, 3-20-00, 3-27-00, and 4-3-00.
Kent, Riegel's Handbook of Industrial Chemistry, pp. 598-622.
Wittcoff and Reuben, Industrial Organic Chemicals in Perspective. Part
Two: Technology, Formulation, and Use, pp. 126-142.