12

Styrene-Butadiene Rubber Adhesives

C.A. MIDGLEY*
BASF Corporation
Chattanooga, Tennessee
AND
J.B. REA
Polysar Limited, Sarnia, Ontario
Canada N7T 7VI

INTRODUCTION tured in North America was produced in sev-

eral plants under government programs and was
Perspective
known as GR-S (government rubber-styrene).
Adhesives have long represented a market, al- After the war the production facilities were sold
beit relatively small, for styrene-butadiene rub- to private enterprise and the product became
bers. The original commercial SBR was used known as SBR.
successfully in this application and today all of The wartime SBR was essentially a single
the SBRs, solution types as well as hot and cold grade multi-purpose rubber. Relative to natural
emulsion types, are used in a variety of adhe- rubber it was deficient in tensile strength, elon-
sive compositions. They are used by adhesive gation, resilience, hot tear, and hysteresis. On
formulators as latexes or as solid rubbers. the other hand it represented an advance over
In 1985 the consumption of SBR in the natural rubber in such key characteristics as
United States was about 1.8 billion pounds. Of abrasion resistance, aging and product uni-
this, about 64 % was used in the manufacture formity.
of tires and related products. Although SBR is Following World War II the focus on SBR
significant among the polymers used in adhe- turned to development of specific products
sives, less than 1% of the total SBR consump- demonstrating improvement in selected prop-
tion was accounted for by this end use. erties over natural rubber as well as the original
SBR. The first such development was the emul-
History of SBR sion polymerization of styrene and butadiene at
low temperature in the presence of a redox cat-
Styrene-butadiene rubber first established its alyst system. The product from this type of
industrial importance during World War II, process represented a marked improvement
when it played a key role as a substitute for over natural rubber in tread stocks for passen-
natural rubber which was in short supply. The ger car tires. Subsequently, application of or-
original styrene-butadiene rubber manufac- ganolithium catalysis permitted development of
solution-polymerized SBRs that offered im-
*Fonnerly with Polysar provements over emulsion SBR in curing rate

I. Skeist (ed.), Handbook of Adhesives

227
© Van Nostrand Reinhold, New York, NY 1990
228 HANDBOOK OF ADHESIVES
and abrasion resistance, although the short sty-
rene blocks characteristic of these polymers ad-
versely affected resilience in tire applications.
Manufacture of SBR
The process of manufacturing styrene-buta-
diene rubber consists of three distinct steps:
polymerization, monomer recovery, and
finishing. The basic characteristics of the poly-
mer, which are outlined below, are determined
in the polymerization step, and the product
form, whether latex or dry rubber, oil extended
or not, is a function of the finishing process.
Basic Chemistry of SBR
SBRs are produced by addition copolymeriza-
tion of styrene and butadiene monomers in
either an emulsion or a solution polymerization
process. The ratio of styrene to butadiene con-
trols the glass transition temperature (Tg) of the
copolymer and thus the stiffness of the elasto-
mer. The higher the styrene content, the higher
the Tg and stiffness. Polymers can be made over
the whole range of Tg from about -80°C for
polybutadiene to about + lOO°C for polysty-
rene.
Because butadiene has two double bonds, two
modes of addition can take place: 1,2 and 1,4.
The 1,2 addition yields a pendent vinyl group
on the growing chain, which increases Tg • The
1,4 addition can occur with the polymer chains
cis or trans to the residual in-chain double
bond. The more regular trans configuration
leads to better cured tensile properties.
The microstructure of the elastomers can be
controlled by the manufacturing process. In
emulsion polymerization, which is a free radi-
cal process, the proportion of cis and trans
structures can be varied by changing the tem-
perature of polymerization. High trans (about
70% of polybutadiene) results at low tempera-
tures (about -lO°C) and higher cis at high
temperatures, where the trans content can drop
to about 50% (at about lOO°C). The pendent
vinyl content remains fairly constant at about
20%. The presence of styrene in the system has
little effect on the relative proportions of the
different butadiene structures in the polymer.
In solution SBR the pendent vinyl content can
be varied from 10 to 90% by choosing a sol-
vent system of an appropriate polarity or by
complexing the catalyst with ether.
A random solution SBR will have almost
equal amounts of cis and trans configuration,
but this can be varied. For example, a change
in catalyst composition can increase the trans
content to 70 %.
The double bond in butadiene-derived mac-
romolecules can be subject to attack by the free
radicals in the emulsion polymerization reac-
tion. Growing chain radicals can propagate
through the double bond of an already formed
chain so that two chains become joined or
crosslinked. If this process is allowed to con-
tinue, more and more chains become linked to-
gether until all molecules become linked to all
other molecules and the molecular weight ap-
proaches infinity. Such structures are called
gels. The amount of crosslinking and the gel
content of the polymer can be controlled in
emulsion polymers by the polymerization tem-
perature, the extent of conversion of monomer
to polymer, and the use of chain transfer agents
(so-called modifiers). High reaction tempera-
tures enhance the crosslinking reaction.
Initiation of the solution SBR reaction is very
rapid in comparison with chain propagation,
and because there is little termination or chain
transfer, a very narrow molecular weight dis-
tribution may be produced. Broadening can be
achieved by use of polar additives and contin-
uous rather than batch polymerization pro-
cesses. The molecular weight can be influenced
by the monomer-to-catalyst ratio. Branching
and crosslinking can be encouraged by the ad-
dition of a third monomer or branching agent,
such as divinyl benzene or tin tetrachloride.
SBR LATEXES IN ADHESIVES
General
An important feature of latexes is that they are
sold and used as such. This means that in most
applications the consumer does not normally
have the opportunity to modify latex properties
before use. In dry rubber systems the molecular
weight of the polymer is modified by the con-
sumer to his specific needs by milling, masti-
cation, etc. Hence a few grades cover a
multitude of applications. This flexibility gen-
erally is not possible with latex. The desired