Formulating PUR foam
cataly.st systems for
the CFC-free era
BY S H U I C H I O K U Z O N O " , D O N A L D W . L O W E * * , AND H I R O Y U K I Y O S H I M U R A * * *
..............................................................................................................................
driving force i n polyure-
thane foam technology is
the regulatory mandate to
develop, by 1995, foam
systems free of chlorofluorocarbons
or with substantially reduced CFC
content. Achieving this will depend
o n qualitative a n d quantitative
changes in the major urethane raw
materials, polyols and isocyanates.
Even more i n s t r u m e n t a l w i l l be
similar changes i n auxiliary inter-
mediates like tertiary amine cata-
lysts and foam stabilizers.
The amine catalysts required by
today's CFC-reduced or CFC-free for-
mulations are likely to be complex blends designed
to accomplish a wide range of tasks like blowing,
gelling, and curing-either immediately or with de-
layed action. Depending on the applications, these
catalysts typically cost 25 to 50% more than their
conventional counterparts. (Both new catalysts and
conventional ones are added at levels of 0.5 to 1.0
parts-by-weight [p.b.w.] to 100 parts polyol.) And
the non-CFC catalysts must frequently be supple-
mented with other intermediates such as foam soft-
eners and stabilizers.
Tailoring additives to products
For flexible foams, i n which CFCs have typically
been employed as auxiliary blowing agents, the re-
quired modifications in the package of additives de-
pend largely on the intended end products. In the
manufacture of low-density slabstock foams, howev-
er, entirely water-blown systems have not yet been
perfected and CFCs are being replaced instead by
methylene chloride blowing agents. Little modifica-
tions in additives have been required in this case.
*Project manager, Chemical Research Laboratory, Tosoh Corp., Shin-
nanyo, lapan.
**Marketing manager for amines and urethanes, North America, South
America, and Mexico, Tosoh U.S.A. Inc., Atlanta, GA.
***Product development manager, Tosoh Corp., Shinnanyo, Japan.
1 : Numbers in parentheses designate references at end of article.
In the production of entirely wa-
ter-blown, high-resiliency (HR)
foam systems based on 4,4'-
diphenylmethane diisocyanate
(MDI), the water, typically added at
levels up to 4 p.b.w., produces
problems such as an increase in
foam density, indentation load de-
flection (ILD) hardness, and blister-
ing or surface-skin deformation; it
also results in poor cure profile
and a narrowing of processing
range.
The high foam density is due
largely to unstable foaming pro-
duced by the use of standard amine
blowing catalysts such as bisdimethy-
laminoethylether at the relatively high levels re-
quired by water-blown systems. Eliminating such
uncontrolled foaming requires the use of stronger-ac-
tivity gelling catalysts than the triethylenediamine
(TEDA) typically used with CFC formulations (1)l.
Fig. 1 shows the greater efficacy of a stronger-activity
gelling catalyst compared with conventional TEDA
catalyst in keeping foam density low in an all-MDI,
HR water-blown system at different isocyanate levels.
For entirely water-blown, hot-cured flexible foam
systems, reducing the unacceptably high foam densi-
ty and ILD hardness is done by adding special soften-
ing additives such as silicone surfactants, or (when
water levels exceed 4 p.b.w.) by replacing the stan-
dard poly01 ingredients in the formulations with
polyols that have high concentrations of ethylene
oxide (EO).
The lowering of hardness and density with high-
EO polyols, however, takes place only within a nar-
row window of concentrations of the organotin co-
catalysts freqiwntly used with the amines. At high ~~~~ ~
tin levels, the high-EO polyols cause unacceptably
high foam densities; at low tin levels, the polyols
cause air flow in the foam to decrease, which hin-
ders resiliency.
To widen the range of tin concentrations over
which the EO polyols can be used, it is necessary to
MODERN PLASTICS. November 1992 73

supplement the polyols with strong-gelling
tertiary amine catalysts of the type already
shown to be effective with water blown, all-
. _ u
gelling catalysts are formulated to stabilize the foam-
ing state and provide low foam densities within a
wide range of tin levels i n a hot-molded flexible
foam system. They also maintain adequate air flow
even at high tin concentrations.
In the case of integral skin foam (ISF), used par-
ticularly in steering wheels, CFC elimination-al-
ready implemented i n many automotive urethane
foam products in 1992-has been harder to accom-
plish. The reason is that condensation or liquefac-
tion of CFCs have traditionally been utilized for the
skin formation on the surface layer of the foam.
Nonetheless, it is possible to improve skin forma-
tion i n all-water ISF systems by changing the nature
and type of the poly01 and polyisocyanate raw ma-
terials. Quality, however, still falls short of that de-
rived from CFC systems.
CFC phase-out i s slow in rigid foams
Although the elimination of CFCs has gone far i n the
case of flexible foams, progress has been slower in
rigid foams. The reason is that such products, which
are widely used as insulating agents, rely on the CFC
to provide the necessary low thermal conductivity.
Nonetheless, rigid foam systems that use only 50%
as much CFC as before, with water (up to 4 p.b.w.)
employed as a co-blowing agent, have become popu-
lar. Among the more environmentally benign alter-
natives to CFC in rigid foam systems now being in-
vestigated are hydrochlorofluorocarbon composi-
tions, particularly HCFC-141b.
The relative increase in the water level in partial-
ly water-blown rigid foam formulations may result
in such adverse properties as low friability, poor di-
mensional stability at high temperatures, and high
K-factors (poor insulating properties). The main
cause of these problems is aggregation in the poly-
mer chains of polyureas formed as by-products of
the water-induced blowing reaction. Such aggrega-
t i o n s occur w h e n t h e
gelling reactions d o n o t
keep pace with the blow-
ing reactions.
O n e way t o redress a
blowing-gelling imbalance
is to e m p l o y stronger-
gelling agents than the TE-
DA used in ordinary CFC- - ra, H., Arai, S., and Lowe,
blown rigid foam systems.
A t y p i c a l strong-gelling
catalyst improves not only
friability of a rigid foam at 301- .-
high water levels but also 40
its adhesive strength (3),
Tnstltyltnr dlaminr*
w h i c h is ,important i n
structural foam applica-
tions. But such additives Fig. 1 : Strong-gelling catalyst lowers density.
74 MODERN PLASTICS, November 1992
,,
can reduce flowability of the formulation,
which can interfere with mold filling.
Therefore, still other blowing catalysts,
added to boost flowabilitv.
The other drawback of"partially water-blown rigid ~ ~~~
foams-low thermal conductivity-is usually ad-
dressed by adding appropriate silicone stabilizers at
levels of about 1.5 p.b.w.; such additives reduce cell
sizes in the foams and thereby improve their heat
conduction.
Finally, the low dimensional stability that is com-
mon with partially water-blown rigid foams can be
remedied by use of the high-efficiency pentamethyl-
diethylenetriamine blowing catalyst that is typically
added to these formulations. This catalyst functions
by improving the uniformity of cell structures. But it
should be noted that excessive amounts of it can en-
large cell sizes to the point where thermal conduc-
tivity is sacrificed.
Replacement of CFC in partially water-blown rigid
foam systems with HCFC causes delays in blowing
that yield foams with poor flowability, high density,
and poor dimensional stability at low temperatures.
Because these problems become more pronounced
with increasing water levels, it is possible to reduce
them to manageable levels by keeping water quanti-
ties below 2 p.b.w. At such low water levels, howev-
er, flowability and the necessary formation of fine
cell structures can suffer. Specially formulated
amine catalysts that produce rapid cell nucleation
and growth prior to gelling are effective in compen-
sating for these deficits.
As can be seen, choosing the appropriate catalysts
and other additives in the era of CFC-free urethane
foam formulations is a complex task that depends on
the nature of the poly01 and isocyanate raw materi-
als, the particular mix of blowing agents, and the
end-use applications of the pfoducts. The constant
tradeoffs between contradictory properties require a
judicious blend of catalyst components to strike an
optimum balance of performance and cost.-Edited
by Gordon GraffO
References
1. Yoshimura, H., Oku-
zono, S., Arai, S., and
Lowe, D.W. Journal of
Cellular Plastics; Vol. 26;
389 (1990).
2. Okuzono, S., Yoshimu-
High- activity gelling catalystD D.W.; Journal of Cellular
Plastics; Vol. 28; 130
(1992). ~~
___ -__ __ ~ _I 3. Okuzono, S., Tamano,
60 80 100 120 Y., Arai, S., and Lowe,
Isocyanate index
D.W.; Proceedings, SPI
32nd Annual Technical-
Marketing Conference;
610 (1989).