Chemico-Biological Interactions 135– 136 (2001) 169– 173

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Overview of isoprene monomer and

polyisoprene production processes
A. Philip Leber *
The Goodyear Tire and Rubber Company, 1485 E. Archwood A6e., Akron, OH 44306, USA

Abstract

Isoprene monomer is employed in the manufacture of polyisoprene and various copoly-

mers (with isobutylene, butadiene, styrene, other monomers). Recent surveys of air levels of
isoprene in US monomer and polymer manufacturing facilities have demonstrated TWA
concentrations B1 ppm in 90% of collected samples, and 98% were B10 ppm. Tumorigenic
responses have been observed in isoprene-exposed rodents. However, the relevance of these
findings to health in occupational environments can only be assessed following completion of
additional and ongoing mechanistic research. © 2001 Elsevier Science Ireland Ltd. All rights
reserved.

Keywords: Isoprene; Polyisoprene; Industrial hygiene; Occupational exposure

1. Introduction

Isoprene is 2-methyl butadiene formed in and/or emitted from numerous natural

sources. The chemical is a precursor to a variety of intermediates found in plant
and animal metabolism. It is the basic monomeric unit in natural rubber, and the
chemical is used predominantly in the manufacture of polyisoprene and various
copolymers such as butyl rubber. Currently, isoprene monomer is separated from
petrochemical streams formed in the production of ethylene.
This paper includes an abbreviated description of the production and manufac-
turing processes for isoprene monomer as well as polyisoprene, plus a summary of
air monitoring data derived from occupational settings.

* Tel.: + 1-330-7961046; fax +1-330-7961069.

E-mail address: apleber@goodyear.com (A.P. Leber).

0009-2797/01/$ - see front matter © 2001 Elsevier Science Ireland Ltd. All rights reserved.
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170 A.P. Leber / Chemico-Biological Interactions 135–136 (2001) 169–173

1.1. Background

During the first millenium, rubber game balls were used by the Mayans in the
Western Hemisphere. They were thought to have developed these ‘toys’ from latex
derived from Hevea trees native to Central and South American. The alkaline latex
was coagulated to generate a rubber matrix from which balls and other articles
were formed. Soot from fires used to heat and soften the rubber may have led to
the finding of the contribution of carbon black as a means of providing toughness
to rubber articles [1].
As rubber was recognized to exhibit a variety of valuable physical properties,
investigators in the 1700s began to assess natural rubber dissolved in solvents to
impart water proofing to fabrics, and to develop materials for elastic goods and hot
air balloons. M. Faraday in 1826 analyzed the chemical nature of rubber, and
found it to consist of carbon and hydrogen. Heating led to a charred residue plus
a hydrocarbon distillate with an empirical formula C5H8. The volatile fraction was
characterized in England in 1860 as having a boiling point of 37– 38°C, and was
termed isoprene. The structure of this chemical was determined in 1882 by W.
Tilden, when he studied volatile fractions isolated from both natural rubber and the
wood product turpentine. Tilden found isoprene became ‘rubbery’ either after
prolonged storage or following contact with certain chemicals [1].
In 1910, the first catalyst employed for isoprene polymerization was metallic
sodium. However, polyisoprene was not immediately a commercial success as
butadiene tended to replace isoprene in polymer production. Interest in synthetic
polyisoprene rubber was enhanced by the development of effective catalysts.
Firestone and BF Goodrich began to manufacture polyisoprene in mid 50s with
Shell and Goodyear following in the early 1960s.
Natural rubber displays many properties that ensure its place as a major source
of elastomer for commercial products. The polymer is 100% cis 1,4 polyisoprene,
and has a high molecular weight (\ 10 million), whereas synthetic polyisoprene has
a slightly lower percentage of the cis 1,4 isomer, and lower average molecular
weights (B1 million). These properties impart higher crystallinity to natural
rubber, which in turn leads to enhanced heat dissipation properties desirable for
truck and aircraft tires. The allergenicity of plant proteins retained in commercial
natural rubber products has been detrimental to its use in certain medical and
consumer products.

1.2. Monomer and polymer production

Isoprene received little commercial attention until the 1950s, when the monomer
was first economically produced. The need for high purity monomer for polymer
production led to improved separation processes. Polymer grade isoprene monomer
exceeds 99% purity. Commercial production involves separation of isoprene
monomer from C5 ethylene by-product streams through a series of fractionation
and extraction distillation steps. Isoprene is one of multiple materials derived from
purification of ethylene byproduct streams that yield C3 and higher olefinic
 A.P. Leber / Chemico-Biological Interactions 135–136 (2001) 169–173 171

products. p-tert-butyl catechol (antioxidant) is added to isoprene to stabilize the

monomer.
The production of polymer entails multiple steps as displayed in Fig. 1. Polymer
formation occurs by reacting monomer in the presence of catalyst in hydrocarbon
(hexane) solution. The process is terminated with the addition of a ‘shortstop’.
Stabilization of the polymer is enhanced with the addition of an antioxidant.
Subsequent steps in the process include stripping of the solvent, water washing of
the polymer to remove catalyst and shortstop residues, and finally pressing and
formation of crumb rubber into bales of product. Bales are covered with plastic
wrap, boxed, and subsequently moved to warehouses.

1.3. Airborne monomer

Isoprene monomer is included on US Environmental Protection Agency’s list of

Clean Air Act’s Volatile Organic Chemicals. In addition, the ‘reportable quantity’
for this ‘hazardous substance’ in EPA’s Superfund program is 100 lb, and is
considered a ‘hazardous substance’ within the US Clean Water Act. However,
isoprene has not been designated a compound of concern by standard-setting
organization in occupational settings. Neither the Occupational Safety and Health
Administration nor the American Conference of Governmental Industrial Hygien-
ists has proposed standards or guidelines. In response to a lack of formal guidelines
for this chemical, the American Industrial Hygiene Association has established a
WEEL (Workplace Environmental Exposure Level) for isoprene of 50 ppm for 8 h.
In order to better assess occupational exposures within monomer/polymer pro-
duction locations within the US, data from three of the major producers were
collected and summarized (Table 1) by the International Institute of Synthetic
Rubber Producers [2]. Key information includes the fact that a total of 325 workers
are employed in monomer and polymer production areas for these major manufac-
turers, and that less than 3% of all time-weighted-average samples (\ 4 h) collected
were above 5 ppm. Personal and area sampling values are combined in this table.
Further assessments were performed at one producer’s plant (Goodyear’s Beau-
mont facility) that produces both monomer and polymer (Table 2). The data
collected during 1999– 2000 indicate that the highest levels of monomer are found

Fig. 1. Schematic for production of polyisoprene.

172 A.P. Leber / Chemico-Biological Interactions 135–136 (2001) 169–173

Table 1
Isoprene air monitoring results from three US isoprene monomer and polymer production facilitiesa

Monomer (ppm) % of samples

B1 91.3
55 97.1
\5 2.9

a
Results for 426 monitoring trials (area and personal values) in three plants during 1992–1997; 325
people worked in the facilities [2].

Table 2
Air levels of isoprene in monomer and polymer production areasa

Plant area c Samples Findings (ppm)

Monomer production 165 66%B1

86%B5
2%\10
Polymer production 115 96%B1
100%B10
Polymer warehouse 8 Non-detect
(0.008)

a
Results for Goodyear plant (Beaumont, TX) [3].

in monomer production areas of the plant [3]. Only 2% of the collected samples
indicated air levels exceeding 10 ppm. Levels in the polymerization area of the plant
were largely below 1 ppm while monitoring within the warehousing area indicated
non-detectable levels.

2. Conclusions

Air monitoring data presented were collected at three US facilities that produce
isoprene monomer and/or polymers. There are few data indicating levels above 10
ppm, and these are only in the monomer production areas. The preponderance of
findings for polymerization areas indicate isoprene air concentrations below 1 ppm.
No measurable amounts of airborne monomer were detected in the warehousing
area, indicating that potential inhalation exposures from handling isoprene poly-
mers are likely to be negligible.

References

[1] H.M. Lybarger, Kirk-Othmer Encyclopedia of Chemical Technology, Isoprene, vol. 14, Fourth ed.,
Wiley, New York, NY, 1995, pp. 934 – 952.
 A.P. Leber / Chemico-Biological Interactions 135–136 (2001) 169–173 173

[2] J.L. McGraw, Letter to the US National Toxicology Program. Information on the scope of human
exposures to workers in the monomer/polymer industry in the US. June 24, 1998.
[3] The Goodyear Tire and Rubber Company. Industrial hygiene data. August 2000.