Note: Descriptions are shown in the official language in which they were submitted.
CA 02578826 2007-03-06
01-2371A
PROCESS FOR THE PREPARATION
OF POLYOL POLYMER DISPERSIONS
Technical Field
This application is a division of Canadian Patent
Application Serial No. 2,188,965, filed October 28, 1996.
The present invention pertains to a process for the
manufacture of polymer polyols by the in situ
polymerization of vinyl monomers and to the manufacture of
polymer-modified polyols by the in situ polymerization of
polyisocyanates and isocyanate reactive monomers, both
types of in situ polymerization conducted in the presence
of a polyoxyalkylene polyether base polyol. More
particularly, the present invention pertains to an improved
process for manufacture of polymer polyols and polymer-
modified polyols having substantially no catalyst residues
in the continuous polyol phase wherein certain double metal
cyanide complex-catalyzed polyoxyalkylene polyether polyols
are used as the base polyol, and the in situ polymerization
are conducted subsequently without removal of double metal
cyanide complex catalyst residues. Polyurethane foams
prepared from such polyol polymer dispersions surprisingly
require less catalyst concentration than similar foams
prepared froni dispersions employing conventional polyols as
base polyols.
Thus, the present invention also pertains to a process
for producing a polyurethane foam wherein the catalyst
level is reduced while retaining similar catalytic
activity, by employing as the polymer polyol component, a
polymer-modified polyol prepared by polymerization of the
dispersed phase in a double metal cyanide complex catalyzed
polyol which contains transition metals derived from the
catalyst.
CA 02578826 2007-03-06
O1-2371A - lA -
Preferably, the method involves. reducing the amount of
catalyst required to prepare a polyurethane foam by the
reaction of an isocyanate component with a polyol component
in the presence of an effective amount of a blowing agent
and one or more urethane reaction promoting catalysts. The
polyol component is preferably a polyol component
containing a polymer-modified polyol prepared by the in
situ polymerization of one or more di- or polyisocyanates
with one or more isocyanate-reactive monomers in an
encapsulative double metal cyanide complex-catalyzed
polyoxyalkylene polyether base polyol. The polymer-modified
polyol contains about 4 ppm or more of transition metals
derived from said encapsulative double metal cyanide
complex used to prepare the base polyol, about 60% or more
of the transition metal content associated with the
dispersed phase particles. It is preferred, as with other
embodiments of the subject invention, that a substantial
amount, i.e., about 60% or more and preferably about 75 %
or more of the total transition metal content be associated
with the dispersed phase. Most preferably, the continuous
phase contains about 1 ppm of each transition metal or
less.
Background Art
Polymer polyols, as that term is used herein, refers
to polyvinyl polymer dispersions prepared by the in situ
polymerization of one or more vinyl monomers in a
polyoxyalkylene "base" polyol. Polymer-modified polyols,
as that term is used herein, refers to
CA 02578826 2007-03-06
01-2371A -2-
polyoxyalkylene polyether polyols having a dispersed
phase of a urea or urethane/urea polymer prepared by the
in situ polymerization of a diisocyanate or
polyisocyanate with an isocyanate-reactive monomer,
preferably an amino-functional monomer such as an
alkanolamine, diamine, or the like. The majority of
such polymer polyols and polymer-modified polyols are
used in the polyurethane field for diverse applications,
including cell openers and hardness enhancers for
polyurethane foam, and as reinforcing additivcs ~
for a
variety of microcellular and non-cellular polyurethanes.
The manufacture of polymer polyols is by now
well known, and may involve batch, semi-batch, and fully
continuous processes. In all of these processes, one or
more vinyl monomers such as acrylonitrile and styrene
are polymerized in situ in one or more base polyols,
with or without the presence of an added stabilizer.
The amount of monomer(s) fed to the reactor is selected
to achieve the desired vinyl polymer solids content in
the final polymer polyol product. The solids level may
range from as little as 5 weight percent to upwards of
60 weight percent, however, it is most economical to
produce polymer polyols at relatively high solids
loadings even when a low solids product is desired. If
a lower solids content polymer polyol is desired, the
solids content may be lowered by dilution of the higher
solids polyol with further amounts of the same base
polyol or other non-polymer polyol, or by blending with
a polymer polyol of lesser solids content. The base
polyol functionality is dictated by the particular
polyurethane end-use desired, and may typically involve
nominal functionalities of two to eight. The details of
polymer polyol manufacture will be presented hereafter.
CA 02578826 2007-03-06
01-2371A -3-
The manufacture of polymer-modified polyols is
also by now well known. The two most common polymer-
modified polyols are the so-called PIPA (PolyIsocyanate
PolyAddition) polyols and the PHD (PolyHarnst off
Dispersion) polyols. Both these polymer-modif ied
polyols and others are prepared by the addition
polymerization of an isocyanate, for example a di- or
polyisocyanate, with an isocyanate-reactive monomer,
preferably an amino-functional compound: an alkanolamine
in the case of PIPA polyols, and a di- cr polyamine in
the case of PHD polyols. Mixtures of these isocyanate
reactive monomers as well as reactive diols may also be
used. The reactive monomers are polymerized in situ in
a polyoxyalkylene polyether polyol which forms the
continuous phase of the polymer-modified polyol. In
many cases, a portion of the polyol continuous phase
becomes associated with the polymer phase by reaction
with isocyanate groups. More detailed description of
polymer-modified polyols is presented hereinafter.
In both polymer polyols and polymer-modified
polyols, the monomers are generally initially soluble in
the polyol continuous phase, as are in general the
initial low molecular weight oligomers. However, as the
molecular weight of the polymer phase grows, the polymer
becomes insoluble, forming small particles which rapidly
coalesce and/or agglomerate to larger particles in the
submicron to several micron range. Hereinafter, the
term "polymer polyol" will refer to dispersions of vinyl
polymers, "polymer-modified polyol" to polyurea,
polyurethaneurea, or other isocyanate-derived polymer
dispersions, and the term "polyol polymer dispersions"
will refer to both of these collectively.
CA 02578826 2007-03-06
01-2371A -4-
The base polyols used in preparing po l yol
polymer dispersions generally contain a high proportion
of polyoxypropylene moieties. Polyoxypropylene
polyether polyols are conventionally prepared by the
base-catalyzed oxyalkylation of a suitably functional
initiator molecule with propylene oxide or a mixture of
propylene oxide and ethylene oxide. During base-
catalyzed oxypropylation, a competing rearrangement of
propylene oxide into allyl alcohol continually
introduces this unsaturated monol into the
polymerization reactor. The allyl alcohol acts as an
additional initiator, and being monofunctional,lowers
the actual functionality of the polyol. The continued
creation of low molecular weight monofunctional species
also broadens the molecular weight distribution. As a
result of these effects, the practical upper limit of
polyoxypropylene polyether polyols equivalent weight is
c.a. 2000 Da (Daltons).
For example, a 4000 Da molecular weight base-
catalyzed polyoxypropylene diol may contain 0.07 to 0.12
meq. unsaturation per gram polyol, amounting to from 25-
40 mol percent of monol. As a result, the polyol
nominal functionality of two is reduced to actual
functionalities of c.a. 1.6 to 1.7 or less.
Unsaturation is generally measured in accordance with
ASTM test D-2849-69 "Testing Urethane Foam Polyol Raw
Materials."
Lowering the oxypropylation temperature and
decreasing the amount of basic catalyst allows for some
reduction of unsaturation, but at the expense of greatly
extended reaction time which is not commercially
acceptable. Moreover, the reduction in unsaturation is
CA 02578826 2007-03-06
01-2371A -5-
but slight. Use of alternative catalyst systems, for
example cesi,im hydroxide rather than the more commonly
used sodium or potassium hydroxides; strontium or ba r ium
hydroxides; dialkyl zinc; metal naphthenates; and
combinations of metal naphthanates and tertiary am i nes
have all been proposed. However, the unsaturation is
generally reduced only to about 0.03 to 0.04 meq/g by
these methods, still representing 10-15 mol per c ent
monol. In all these cases, the catalyst residues must
be removed prior to the in situ polymerization of v i n-vi
or other monomers to produce polyol polymer dispersions.
Basic catalysts are generally removed by adsorption with
magnesium silicate followed by filtration, by
neutralization followed by filtration, or through the
use of ion-exchange techniques.
In the 1960's, double metal cyanide catalysts
such as complexes of zinc hexacyanocobaltate were found
to be useful in a variety of polymerization reactions,
as evidenced by U.S. Patent Nos. 3,427,256, 3,427, 334,
3,427,335, 3,829,505, 3,941,849, and 4,242,490. In
polymerization of propylene oxide, such catalysts were
found to produce polyols with unsaturation in the range
of 0_02 meq./g. However, even though relatively active
catalysts, their cost relative to activity was quite
high. In addition, catalyst removal was problematic.
Refinements in double metal cyanide complex cata l ysts
have led to catalysts with somewhat higher activity, as
evidenced by U.S. Patent Nos. 4,472,560, 4;477,589,
4,985,491, 5,100,997, and 5,158,922. These catalysts,
generally glyme complexes of zinc hexacyanocobal t ate,
were effective in preparing polyoxypropylene po l yols
with unsaturation levels of c.a. 0.015 to 0.018 me q/g.
Despite being more active than the prior catalysts, the
CA 02578826 2007-03-06
01-2371A - 6 -
cost of these improved catalysts, in addition to the
difficulties associated with catalyst removal, again
prevented any large scale commercialization.
Recently, however, exceptionally active double metal
cyanide complex catalysts have been developed at the ARCO
Chemical Co., as evidenced by U.S. Patents 5,470,813 and
5,482,908. In addition to their much higher activity as
compared to previous double metal cyanide complex
catalysts, these catalysts have further been shown suitable
for producing polyoxypropylene polyols with measured
unsaturation in the range of 0.003 to 0.007 meq/g. Not
only is the measured unsaturation exceptionally low, but
moreover, despite the fact that unsaturation is generally
accepted as a measure of monol content, lower molecular
weight species are not detected by gel permeation
chromatography. The polyoxypropylene polyols are truly
monodisperse, having a very narrow molecular weight
distribution. Despite being much more active catalysts
than prior catalysts and being more susceptible to simple
filtration for catalyst removal, the necessity to finely
filter or otherwise remove catalyst residues prior to use
as base polyols for polyol polymer dispersion production
undesirably increases processing time.
In Japanese published application H2-294319 (1990),
double metal cyanide complex catalysts were used to prepare
polyoxypropylene polyols following which the doubi-e metal
cyanide catalyst residues were denatured by adding alkali
metal hydroxide which then served as the oxyalkylation
catalyst for capping the polyoxypropylene
CA 02578826 2007-03-06
01-2371A -7-
polyols with oxyethylene moieties. Following removal of
the catalyst residues, high primary hydroxyl content
polymer polyols were prepared in a conventional manner.
Similar polymer polyols prepared by in situ
polymerization in oxyethylene capped polyoxypropylene
polyols are disclosed in U.S. Patent Nos. 5,093,380 and
5,300,535.
In Japanese published application 5-39428
(1993), unspecific zinc hexacyanocobaltate catalyGte
were used to prepare polyoxypropylene polyols which were
then used as base polyols for polymer polyol manufac-
ture, with or without further addition of double metal
cyanide catalyst as a vinyl polymerization catalyst.
However, the presence of large amounts of double metal
cyanide catalyst residues in the polymer polyol product,
even if they did not affect subsequent in situ vinyl
polymerization, is undesirable. In the food processing
industry and medical prostheses industries, for example,
heavy metal ion content must be minimal.
J.L. Schuchardt and S.D. Harper, "Preparation
Of High Molecular Weight Polyols Using Double Metal
Cyanide Catalysts, " 32ND ANNUAL POLYURETHANE TECHNICAL MARKETING
CONFERENCE, Oct. 1-4, 1989, discloses that double metal
cyanide complex catalyst residues can increase the
viscosity of isocyanate-terminated prepolymers prepared
from polyols containing such residues, this viscosity
increase-be-lieved due to allophanate formation. Herrold
et al. in U.S. Patent No. 4,355,188 and the many other
patents directed to removal of catalyst residues, e.g.,
U.S. Patent Nos. 3,427,256, 5,248,833, 4,721,818,
5,010,047, and 4,987,271 attest to the commercial
significance of double metal cyanide catalyst removal.
CA 02578826 2007-03-06
01-2371A -8-
It would be desirable to provide a method of
preparing polyol polymer dispersions from double metal
cyanide catalyzed polyoxypropylene polyether polyols
without the necessity of removing or denaturing double
metal cyanide complex catalyst residues, without such
catalyst residues appearing in the continuous polyol
phase of the polyol polymer dispersion. It would be
further desirable to prepare polymer polyols which are
white or off-white in color.
Summary Of The Invention
It has now been surprisingly discovered that
polyol polymer dispersions may be prepared from certain
double metal cyanide complex-catalyzed polyoxypropylene
polyether polyols without removing the double metal
cyanide complex catalyst residues, while obtaining
polyol polymer dispersions containing only exceptionally
low levels of catalyst residues in the continuous polyol
portion of the polyol polymer dispersion. The polymer
polyols of the subject invention are generally white to
off-white in color, and may be stored without concern of
gradual precipitation of double metal cyanide complex
resiaue solids or generation of carbonyl group-contain-
ing polyether polyol decomposition products. Catalyst
levels in polyurethane foam formulations employing
polyol polymer dispersions of the subject invention can
unexpectedly be reduced from levels required for prepar-
foam from dispersions employing conventional polyols
ing
as the base polyol.
CA 02578826 2007-03-06
01-2371A - 9 -
Description Of The Preferred Embodiments
The polyoxyalkylene polyols used as base polyols for
the subsequent manufacture of polyol polymer dispersions
preferably include at least one polyoxyalkylene polyether
polyol prepared by the polymerization of propylene oxide
onto one or more initiator molecules of suitable func-
tionality, optionally in conjunction with one or more
alkylene oxides other than propylene oxide, in the presence
of an encapsulative double metal cyanide complex catalyst
as hereinafter defined. The alkylene oxides other than
propylene oxide which may optionally be used in conjunction
with the latter include, but are not limited to, ethylene
oxide, 1,2- and 2,3-butylene oxide, styrene oxide, C5_20 0-
olefin oxides, epichlorohydrin, chlorinated butylene
oxides, and the like. Ethylene oxide is particularly
preferred. When an additional alkylene oxide other than
ethylene oxide is used together with propylene oxide, the
additional alkylene oxide may be added to the
polymerization at any stage, either alone, or with
additional propylene oxide, to form block, random, or
block/random polyoxyalkylene polyether polyols. However,
when ethylene oxide is used as the additional alkylene
oxide, the ethylene oxide must be added together with
propylene oxide or other higher alkylene oxide to form
random or block/random polyoxyalkylene polyols.
Polyoxyalkylation with ethylene oxide alone has been found
to result in products believed to contain large quantities
of polyoxyethylene instead of the desired oxyethylene
blocks or caps in the polyoxyalkylene polyol.
Suitable initiator molecules include the di- to
octafunctional, conventional initiator molecules, for
CA 02578826 2007-03-06
01-2371A -10-
example, ethylene glycol, propylene glycol, glycerine,
trimethylolpropane, pentaerythritol, sorbitol, sucrose_
and the like. However, it has been found that double
metal cyanide complex-catalyzed oxyalkylation of low
molecular weight initiators, particularly low molecular
weight vicinal glycol initiators such as the foregoing,
results in low initial oxyalkylation rates as well as an
extended "induction period" before significant catalytic
activity occurs. Thus, it is preferable to use oligo-
meric polyox_yalkylar_ion products of the above or other
monomeric initiators as initiators for preparing the
base polyoxyalkylene polyol.
Suitable oligomeric initiators may be prepared
by conventional, base catalyzed oxyalkylation of mono-
meric initiators, or by catalysis with alternative
catalysts such as diethylzinc, calcium naphthenate, and
the like. The particular catalyst is not critical,
however, when basic catalysts are used, the catalyst
residues should be removed from the oligomeric initiator
by conventional treatment prior to continued oxyalkyl-
ation employing double metal cyanide complex catalysts;
otherwise, the latter may be inactivated. The oligomer-
ic initiators may comprise monomeric initiators oxy-
alkylated with propylene oxide, mixtures of propylene
oxide and ethylene oxide or another alkylene oxide,
higher alkylene oxides, or all ethylene oxide. Prefera-
ble are oligomeric initiators prepared from all propyl-
ene oxide - or tnixtures of propylene oxide and ethylene
oxide. The oligomeric initiators preferably have
equivalent weights of from 100 Da to 1000 Da, preferably
from 150 Da to 500 Da. Molecular weights and equivalent
weights herein in Da (Daltons) are number average
CA 02578826 2007-03-06
01-2371A -11-
molecular weights and number average equivalent weights,
respectively, unless otherwise designated.
The oxyalkylation conditions for preparation
of the base polyol are those conventionally used in
double metal cyanide complex oxyalkylation. The initia-
tor, preferably an oligomeric polyoxyalkylene polyol
initiator, is charged to an agitated reactor, the double
metal cyanide complex catalyst added, and the reactor
purged with nitrogen. Propylene oxide is added at the
desired oxyalkylation temperature, generally from 50 C
to 160 C, more preferably from 70 C to 130 C, and the
reactor pressure monitored until a pressure drop is
observed, indicating the end of the induction period.
Additional propylene oxide, optionally in conjunction
with other alkylene oxide, is then added until the
desired molecular weight is achieved. Reaction pressure
is generally kept below 6 bar. Following alkylene oxide
addition, the reactor is maintained at the oxyalkylation
temperature for a period to allow unreacted alkylene
oxide to react, the reactor vented, and any remaining
alkylene oxide stripped off at modest to low vacuum,
optionally with the use of a nitrogen stream.
In the past, following preparation of polyoxy-
alkylene polyols by the above method, the polyol product
has been treated to remove residual double metal cyanide
catalyst, by filtration, denaturing, treatment with
chelating agents, or combinations of these methods.
However, in the practice of the subject invention, it is
not necessary to remove the double metal cyanide complex
catalyst residues to the extent necessary for conven-
tional polyether polyols, provided an encapsulative
double metal cyanide complex catalyst is used. It would
CA 02578826 2007-03-06
01-2371A -12-
not depart from the spirit of the invention to rap i dly
filter the polyoxyalkylene polyol, for example, through
a coarse filter to remove a portion of the cata l yst
residues, or to store the polyol in a non-agitated tank
and allow a portion of the catalyst residues to se t tle
out. However, in either case, the amount of residual
double metal cyanide complex residues present in the
base polyol prior to in situ vinyl polymerization, will
normally exceed the limits detectable by Inductively
Coupled Plasma sample analysis or other equivalent means
of analysis, this limit generally being c.a. 1 ppm.
Preferably, the major portion of double metal cyanide
complex catalyst residue is not removed from the base
polyol.
For example, a polyoxypropylene polyol pre-
pared with an encapsulative zinc hexacyanocobaltate
complex catalyst at a catalyst concentration of 250 ppm
in the finished polyol, after simple filtration or
normal setting upon storage, may contain 47 ppm Zn and
16 ppm Co. Following polymer polyol preparation, the
levels of Zn and Co in the polyol polymer dispe r sion
continuous phase may be reduced to 2 ppm Zn and < 1 ppm
Co, levels which are commercially acceptable. Prepara-
tion of base polyols with encapsulative double metal
cyanide catalysts at lower catalyst levels and/or by
more thorough filtration, with or without addit i onal
methods of catalyst removal, may result in Zn and Co
levels of, for example 3 ppm and 2 ppm, respectively
prior to polymerization to prepare the dispersed phase.
While these transition metal levels are low, they may be
lowered further by in situ polymerization to form
dispersed polymer phase in which the catalyst residues
are concentrated in the dispersed phase.
CA 02578826 2007-03-06
01-2371A - 13 -
Thus, whether the initial transition metal content
is high or low, it is lowered further by the process of
the subject invention, provided that an encapsulative
double metal cyanide complex catalyst is utilized. It
is most surprising that under the same conditions, non-
encapsulative double metal cyanide catalysts remain
substantially in the continuous phase. The subject
process allows encapsulative double metal cyanide
complex catalyst residues to be simply left in the
polyol without any post-treatment catalyst removal, or
post-treatment which removes only a portion of catalyst
residues, for example a coarse, rapid filtration which
by itself would not be suitable for purification of non-
polymer, double metal cyanide complex catalyzed polyols.
The base polyols suitable for use in the process of
the subject invention may contain from 4 ppm transition
metal content to well over several hundred ppm
transition metal content. Preferably, the base polyols
contain from 4 ppm to 100 ppm, more preferably from 5 to
50 ppm, and most preferably, from 10-40 ppm transition
metal content. Catalyst concentrations of 20 ppm or more
relative to base polyol are the general rule, and quite
suitable for use in the subject invention. Preferably,
the base polyol is not treated to remove catalyst
residues. However, if treated, filtration to remove
catalyst residues such that the transition metal content
is greater than about 2 ppm is one preferable means of
CA 02578826 2007-03-06
01-02371A - 13A -
treatment, and sedimentation followed by separation of
catalyst-depleted supernatant constitutes a second
preferable means of treatment. The catalyst remaining in
the continuous phase following in situ dispersed phase
polymerization preferably contains less than 4 ppm total
transition metals, more preferably less than 3 ppm, and
most preferably less of each metal than a lower limit of
detection of c.a. 1 ppm. The advantageous results of
the subject process may also be characterized by the
degree of catalyst removal from the base polyol into the
dispersed polymer phase, regardless of the continuous
phase transition metal content. Preferably, 60% or more
of the transition metal content of the base polyol is
partitioned into the dispersed polymer phase, more
CA 02578826 2007-03-06
01-2371A -14-
preferably 75% or more, and most preferably about 90% or
more on a weight basis. Both a high of percentage
partitioning and minimal continuous phase transition
metal content are of course most desirable.
The polyol polymer dispersions prepared by the
subject process are unique products, in that double
metal cyanide complex catalyst residues are present in
the polymer polyol or polymer-modified polyol as a
whole, but concentrated in the dispersed polymer phase
and largely absent from the continuous polyol phase.
Such polyol polymer dispersions have not been previously
disclosed.
The double metal cyanide complex catalysts
useful in the subject invention are encapsulative double
metal cyanide catalysts. When such catalysts are
utilized, the catalyst residues become associated with
the polymer particle dispersed phase, and are removed
from the continuous polyoxyalkylene polyether polyol
phase. While not wishing to be bound by any particular
theory, it is believed that the polymer particles
actually encapsulate the double metal cyanide complex
catalyst residues. It is possible that the polymeriz-
able monomers preferentially polymerize on or proximate
to the double metal cyanide complex residues, surround-
ing the residue with polymer, or that double metal
cyanide complex particle residues serve as nucleation
sites for polymer particle agglomeration or coagulation,
or that the polymer particles or agglomerates serve as
adsorbent sites for the catalyst residues.
By whatever mechanism or combination of
mechanisms which is/are operable, the net result is that
CA 02578826 2007-03-06
01-2371A -15-
double metal cyanide complex residues are removed f rom
the continuous polyoxyalkylene polyether polyol phase.
When the discontinuous polymer phase is separated f rom
the polyol phase by means of filtration or cent r if-
ugation, it is found that when an encapsulative double
metal cyanide complex catalyst is used, the polymer
particles contain virtually all catalyst residues and
the polyol phase contains little or none. The measured
amounts of transition metals, for example, zinc and
cobalt, in the continuous polyoxyalkylene polyol compo-
nent are close to or below the common limits of detec-
tion. Thus, the term "encapsulative double metal
cyanide catalyst" refers to a double metal cyanide
catalyst which becomes associated with the polymer
particles of the dispersed polymer phase in polyol
polymer dispersions such that no substantial amount of
double metal cyanide catalyst remains in the continuous
polyol phase. At least 75 weight percent of double
metal cyanide complex residues, as measured by total
Zn/Co concentrations, should preferably be removed from
the continuous polyol phase.
It has been surprisingly found that the double
metal cyanide complex catalysts utilized in the prior
art, zinc hexacyanocobaltate=glyme catalysts, are not
encapsulative double metal cyanide catalysts. Residues
of such catalysts, as shown by Comparative Example 5
herein, remain in most substantial part in the continu-
ous polyol phase. To determine whether any particular
double metal cyanide complex catalyst is an encapsula-
tive double metal cyanide complex catalyst, a simple
test may be performed. In this test, the double metal
cyanide complex catalyst under consideration is used to
prepare a polyoxyalkylene polyether base polyol by
CA 02578826 2007-03-06
O1-2371A - 16 -
oxyalkylating a 200-500 Da equivalent weight oligomeric
polyoxypropylene initiator in the presence of from 25 ppm
to 250 ppm double metal cyanide complex catalyst based on
the weight of the base polyol product. The amounts of
transition metals in the polyol product, for example Co and
Zn, are measured, for example by Inductively Coupled Plasma
techniques, and a polymer polyol prepared by the in situ
polymerization of a 1:2 mixture of acrylonitrile and
styrene in the presence of an effective amount of a vinyl
polymerization initiator, for example 0.5 weight percent
azobisisobutryronitrile, to form a polymer polyol having a
dispersed phase which constitutes from 20 to 50 percent by
weight of the polymer polyol product. The dispersed
polymer phase is then separated from the continuous polyol
phase and the transition metal content of the polyol phase
determined. If the polyol phase contains less than 25%
total transition metal as compared to the amount present in
the base polyol prior to in situ vinyl polymerization, or
if regardless of the relative percentage the transition
metal contents of the continuous polyol phase are lowered
from higher levels to approximately the limits of detection
or below (1-2 ppm), then the catalyst is an encapsulative
double metal cyanide complex catalyst. The encapsulative
double metal cyanide complex catalysts identified by this
test may be used to prepare both the polymer polyols and
polymer-modified polyols of the subject invention.
Suitable encapsulative double metal cyanide complex
catalysts are disclosed in U.S. Patents 5,470,813 and
5,482,908. Examples of encapsulative double metal
CA 02578826 2007-03-06
01-2371A -17-
cyanide complex catalysts are given herein in Examples
1-6. While the descriptions herein and test methodology
have been illustrated by the use of the preferred zinc
hexacyanocobaltate complex catalysts, it is to be
understood that encapsulative double metal cyanide
complexes of other metals may be used as well. In such
cases, the definitions, ranges, limitations, etc.,
presented herein with respect to Co and Zn should be
equated with the same limitations for the particular
metals involved, for example Zn and Fe for zinc hexa-
cyanoferrates; Ni and Fe for nickel hexacyanoferrates;
and Fe and Cr for iron(II) hexacyanochromate. Due to
their generally higher catalytic activity, complexes
containing zinc as the cation and cobalt in the cyanide-
containing anion are highly preferred. For purposes of
definition of catalyst residues in ppm, a theoretical
metal atomic weight of 62 is assumed. The corresponding
ppm level for any given metal may be found by multiply-
ing a particular metal residue level by the appropriate
atomic weight/theoretical metal atomic weight ratio.
For example, if the metal were vanadium with an atomic
weight of approximately 51 amu, a 5 ppm metal residual
level would become 5 ppm x(51/62).
Preferred complexing agents for preparing the
encapsulative double metal cyanide complex catalysts are
t-butanol and combinations of t-butanol with one or more
oligomeric polyoxyalkylene polyether polyols, preferably
polyether polyols at least partially terminated with a
tertiary hydroxyl moiety. The polyether polyol complex-
ing agents preferably have equivalent weights greater
than 200 Da, more preferably greater than 500 Da, and
most preferably in the range of 1000 Da to 3000 Da. The
encapsulative double metal cyanide complex catalysts
CA 02578826 2007-03-06
01-2371A - 18 -
are, in general, non-stoichiometric complexes which are
substantially amorphous as shown by the virtual absence
of sharp lines in their X-ray diffraction spectra
corresponding to crystalline double metal cyanide
itself, i.e., zinc hexacyanocobaltate in the case of
zinc hexacyanobaltate complex catalysts. The catalysts
also, in general, have measurably greater particle sizes
than prior art catalysts, such as the conventionally
prepared zinc hexacyanobaltateglyme catalysts.
Preferably used are substantially amorphous zinc
hexacyanocobaltate complex catalysts exhibiting
substantially no sharp peak in an X-ray diffraction
pattern at a di-spacing of approximately 5.1.
The in situ vinyl polymerization used to prepare
polymer polyols is conventional except for the presence
of the encapsulative double metal cyanide complex
residues. Examples of suitable polymer polyol
preparation may be found in U.S. Patent Nos. 3,304,273,
3,383,351, 3,652,639, 3,655,553, 3,823,201, 3,953,393,
4,119,586, 4,524,157, 4,690,956, 4,997,857, 5,021,506,
5,059,641, 5,196,746, and 5,268,418. Either batch
processes, semi-batch, or fully continuous methods of
preparation may be used. Continuous processes are
prefe-rred.
In the semi-batch process, a reactor vessel
equipped with an efficient means of agitation, for
example an impeller-type stirrer or recirculation loop,
is charged with from 30% to 70% of total base polyol.
CA 02578826 2007-03-06
O1-2371A - 18A -
To the reactor is then added the polymerizable vinyl
monomers dissolved in additional polyol. Vinyl polymer-
ization catalyst may be added to the vinyl monomer
solutions, which are maintained at relatively low
temperature prior to addition to the reactor, or may be
added as a separate stream. The reactor itself is
maintained at a temperature such that the polymerization
catalyst is activated. In most cases, the vinyl poly-
CA 02578826 2007-03-06
01-2371A -19-
merization catalyst is a free radical polymerization
initiator. Following addit;.on of the desired quantity
of vinyl monomers, the reactor is allowed to "cook out"
to substantially complete vinyl polymerization, follow-
ing which residual unreacted monomers may be removed by
stripping.
A continuous process may be implemented in one
or more reactors in series, with the second reactor
facilitating substantially complete react_on of vinyl
monomers with continuous product takeoffs, or may be
performed in a continuous tubular reactor with incremen-
tal additions of vinyl monomers along the length of the
reactor.
The preferred vinyl monomers are styrene and
acrylonitrile. However, many vinyl monomers are suit-
able, non-limiting examples being methylacrylate,
methylmethacrylate, a-methylstyrene, p-methylstyrene,
methacrylonitrile, vinylidene chloride, and the like.
Lists of suitable vinyl monomers may be found in the
references previously cited. Mixtures of vinyl monomers
are advantageously used, preferably mixtures of acrylo-
nitrile and styrene in weight ratios of 10:1 to 1:10,
more preferably 1:4 to 4:1, and most preferably 1:1 to
1:3. Mixtures of vinyl monomers comprising about 50
weight percent or more of styrene with one or more
monomers other than styrene are particularly preferred.
The polymerization catalyst is preferably a
free radical polymerization initiator such as an azobis-
alkylnitrile, for example azobis(isobutryonitrile)
(AIBN), azobis(4-cyanovaleric acid), azobis(dimethyl-
valeronitrile), preferably AIBN; peroxy compounds, for
CA 02578826 2007-03-06
01-2371A -20-
example, peroxyesters and peroxyketones, and the like.
Redox polymerization initiators may also be used.
The in situ vinyl polymerization is preferably
conducted in the presence of a stabilizer or stabilizer
precursor. Stabilizer precursors may comprise one or
more polyoxyalkylene moieties bonded to a group which
can participate in vinyl polymerization, preferably a
reactive, unsaturated ethylenic group. Examples of
stabilizers andstabilizer pre~ursors are contained in
the previously cited patents, and include polyetherester
polyols prepared by reacting maleic anhydride with a
polyoxyalkylene polyol and capping the remaining free
carboxyl group of the half-ester with an alkyl or
polyoxyalkyl group; the reaction product of isocyanato-
ethylacrylate or like compounds with a polyoxyalkylene
polyol; or the reaction product of other unsaturated
isocyanates, i.e., TMI, 1-(1-isocyanato-l-methylethyl)-
3-(1-methylethenyl)benzene with a polyoxyalkylene
polyol. The stabilizer precursor may be present in the
reaction mixture to the extent of less than 0.01 to
about 0.3 mol percent, preferably 0.01 to about 0.1 mol
percent.
Reaction moderators and polymer control agents
may also be present. Reaction moderators fall within
the general class of chain transfer agents, and are
believed to limit the molecular weight of the vinyl
polymers produced. Examples of reaction moderators
include alkanols such as isopropanol and isobutanol;
mercaptans such as dodecylmercaptan; halogenated hydro-
carbons, particularly those containing bromine and/or
iodine, and the like. Further examples of reaction
moderators may be found in the patents previously cited.
CA 02578826 2007-03-06
O1-2371A - 21 -
Polymer control agents include low molecular weight
liquids not conventionally viewed as chain transfer agents,
as described in U.S. Patent No. 4,652,589. Suitable polymer
control agents include water, cyclohexane, and benzene.
As previously discussed, polymer-modified polyols are
prepared by in situ polymerization of one or more di- or
polyisocyanates with isocyanate-reactive components, which
may be a portion of the isocyanate itself. For example,
polymerization of a di- or polyisocyanate with itself in
the presence of a suitable catalyst may be used to form
polyisocyanate dispersions (PID), or dispersions containing
a variety of isocyanate-derived linkages such as
isocyanurate, allophanate, uretonimine, uretdione,
carbodiimide and the like, often in association with
reaction of a portion of the polyol continuous phase to
introduce urethane linkages, or when an amino-functional
species is present, urea linkages.
However, the preferred polymer-modified polyols are
those prepared by the in situ polymerization of a di- or
polyisocyanate with an amino-functional monomer, preferably
a diamino-functional monomer, or an alkanolamine monomer,
to form PHD and PIPA polymer-modified polyols. Preparation
of polymer-modified polyols by reaction of
alkanolamine/isocyanate reaction mixtures in situ is
described in U.S. Patent Nos. 4,293,470; 4,296,213;
4,374,209; 4,452,923; and PCT published application WO
94/12553. In general, a mono- to trialkanolamine having
from two to about 8 carbons in the alkanol residue such as
ethanolamine, diethanolamine, triethanolamine,
diisopropanolamine, triisopropanol-amine, N-
CA 02578826 2007-03-06
01-2371A -22-
methylisopropanolamine, 2-(2-aminoethoxy)ethanol,
hydroxyethylpiperazine, or the like is dissolved ir a
polyoxyalkylene base polyol, and di- or polyisocyanate,
preferably TDI or MDI is added dropwise with stirring,
during the course of which the temperature generally
rises to about 40-50'C. Catalysts are generally unnec-
essary, although in some cases catalysts such as stan-
nous octoate or dibutyltin dilaurate may be added. The
reaction is generally allowed to proceed for a period of
from 0.5 to 2 hours, during the course of which a white
dispersion is obtained. In general, a portion of the
polyol will also react, as described in Goethals, Ed.,
TELECHELIC POLYMERS: SYNTHESIS AND APPLICATIONS, CRC Press,
Inc., Boca Raton, FL, m 1989, p. 211.
In PCT published application WO 94/12553 is
disclosed an improved, substantially continuous process
for preparing PIPA polyols with high solids content and
minimal viscosity. In the process disclosed, a polyoxy-
alkylene base polyol is mixed with a first alkanolamine
such as triethanolamine, and fed to a high pressure
mixhead calibrated to provide the desired amount of
isocyanate, preferably polymeric diphenylmethane di-
isocyanate or an 80:20 mixture of 2,4- and 2,6-toluene-
diisocyanates. A short time later, e.g. 5 seconds, a
further quantity of alkanolamine, which may be the same
or different from the first, is added to the reactive
mixture in a second high pressure mixhead. By this
process, stable, non-gelling, high solids dispersions of
useable viscosity are obtained with solids contents in
some cases in excess of 50% by weight.
PHD polymer-modified polyols are also pre-
ferred polymer-modified polyols. Such polyols are
CA 02578826 2007-03-06
-23-
described in Goethals, op.cit., U.S. Patent Nos.
3,325,421; 4,042,537; and 4,089,835; and also in M.A.
Koshute et al., "Second Generation PHD Polyol For
Automotive Flexible Molding", POLYURETHP.NES WORLD= CONGRESS,
1987 - September 29 - October 2, 1987, pp. 502-507; and
K.G. Spider et al., "PHD Polyols, A New Class of P[TR Raw
Materials," J. CELL PLAS., January/February 1981, pp. 43-
4 9.
In general, as with PIPA polyols, the isocyan-
ate-reactive monomer, in this case an amine or poly-
amine, is added to the base polyol. For amines with low
solubility, high speed stirring is used to form a fine
dispersion. Isocyanate is then added slowly, during the
course of which the temperature will rise. Following a
period of time to allow for full reaction, a white,
polyurea dispersion is obtained. The polymer particles
incorporate a portion of the polyol continuous phase.
Preferred diamines are hydrazine and ethylenediamine,
although other diamines as well as hydrazides, are
useful. Preferred isocyanates are commercial aromatic
isocyanates such as methylene diphenylene diisocyanate,
toluene diisocyanate, polyphenylene polymethylene
polyisocyanate, and-the like, including modified iso-
cyanates such as urethane-, urea-, carbodiimide-,
uretdione-, uretonimine-, and allophanate-modified
isocyanates. Aliphatic is.oc.yanates such as hexamethyl-
ene diisocyanate and isophorone diisocyanate are also
useful in manufacturing PHD (and PIPA) polymer-modified
polyols.. Solids levels of 10-40% or more are useful, in
particular .10 or 20 to about 30%. Continuous processes,
as disclosed in U.S. Patent No. 4,089,835 are useful.
CA 02578826 2007-03-06
01-2371A -24-
The base polyol used for in situ polymeriza-
tion to form polyol polymer dispersions should comprise
in major part a polyoxyalkylene polyol containing a sub-
stantial quantity of oxypropylene moieties prepared in
the presence of an encapsulative double metal cyanide
catalyst, preferably at least 5 ppm of which, calculated
as Co and Zn or the corresponding equivalents of other
metals on a weight/weight basis, remain in the polyol.
Preferably, this major component of the base polyol is
not subjected tc catalyst removal treatment other than
an optional coarse filtration to remove gross particula-
tes or by natural sedimentation of catalyst residues in
a non-agitated holding tank. This major portion of
polyoxyalkylene (> 50 weight percent) may be mixed with
other base polyol components such as conventionally
catalyzed polyoxyalkylene polyether polyols, polyester
polyols, polyetherester polyols, and the like. However,
if polyoxyalkylene polyols prepared from non-encapsula-
tive double metal cyanide catalysts are used, either the
non-encapsulative double metal cyanide catalyst residues
must be substantially completely removed, or the amount
of such polyol restricted such that no more than 3-4 ppm
non-encapsulative double metal cyanide complex catalyst
residue calculated on the basis of Co and Zn or their
other-metal equivalents is present in the base polyol.
The functionality of the polyoxyalkylene polyether
polyol component may range from less than two, to eight
or more, preferably from two to eight and more prefera-
bly from two to six. The functionality for any given
base polyol component is dependent on the desired end
use. For example, elastomers generally require low
functionalities, e.g., two to three, while polyurethane
foams generally require functionalities from 2.5 to 4Ø
"Functionality" as used herein is meant the mol average
CA 02578826 2007-03-06
01-2371A -25-
nominal functionality. "Nominal" functionality is the
theoretical functionality based on the number of oxy-
alkylatable groups on the initiator molecule.
The hydroxyl number of the base polyol may
range from about five to in excess of 100, but is
preferably within the range of 10-70, and more prefera-
bly in the range of 20-60. Hydroxyl number may be
measured in accordance with ASTM D-2849-69. The hydroxyl
r.umwer and functionality of the polyol polymer disper-
sion may be adjusted post manufacture by the addition of
polyols other than the base polyol used for the in situ
polymerization. Solids contents of the polyol polymer
dispersions range from about 10 weight percent to about
60 weight percent or more based on total polymer polyol
weight. Polymer polyols are preferably prepared with
solids contents in the higher ranges, i.e., 25 to 60
weight percent, more preferably 30 to 50 weight percent,
and reduced in solids content where appropriate by
blending with additional polyol. In this manner,
reactor capacity and product throughput are maximized.
Polymer-modified polyols generally contain somewhat
lower levels of solids to limit viscosity of the poly-
mer-modified polyol product. Solids contents of from 10
to 50 weight percent, more preferably from 10 to 30
weight percent are suitable.
Double metal cyanide complex catalyst sample
x-ray diffraction spectra were analyzed using mono-
chromatized CuKal radiation (X = 1.54059 A) . A Seimens
D500 Kristalloflex diffractometer powered at 40 kV and
30 mA was operated in a step scan mode of 0.02 2B with
a counting time of 2 seconds/step. Divergence slits of
1 in conjunction with monochrometer and detector
CA 02578826 2007-03-06
01-2371A -26-
apertures of 0.05 and 0.15 respectively. Each sample
was run from 5 to 70 2e. Water of hydration can cause
minor variations in measured d-spacings.
The following procedures may be used to
determine catalyst activity. A one-liter stirred
reactor is charged with polyoxypropylene triol (700 mol.
wt.) starter (70 g) and zinc hexacyanocobaltate catalyst
(0.057 to 0.143 g, 100-250 ppm level in finished
polyol) . The mixture is stirred and heated to 105 C and
is stripped under vacuum to remove traces of water from
the triol starter. The reactor is pressurized to about
1 psi with nitrogen. Propylene oxide (10-11 g) is added
to the reactor in one portion, and the reactor pressure
monitored carefully. Additional propylene oxide is not
added until an accelerated pressure drop occurs in the
reactor; the pressure drop is evidence that the cata-
lyst has become activated. When catalyst activation is
verified, the remaining propylene oxide (490 g) is added
gradually over about 1-3 h at a constant pressure of 20-
24 psi. After propylene oxide addition is complete, the
mixture is held at 105 C until a constant pressure is
observed. Residual unreacted monomer is then stripped
under vacuum from the polyol product, and the polyol is
cooled and recovered.
The reaction rate is determined from a plot of
P0 consumption in grams versus reaction time in minutes.
The slope of the curve at its steepest point is measured
to find the reaction rate in grams of P0 converted per
minute. The intersection of this line and a horizontal
line extended from the baseline of the curve is taken as
the induction time (in minutes) required for the cata-
lyst to become active.
CA 02578826 2007-03-06
01-2371A -27-
Polyurethane foams, particularly water-blown
flexible polyurethane foams, are prepared by reacting a
polyol component with an isocyanate component. The
polyol component often contains a polymer polyol or
polymer-modified polyol, with or without additional non-
polymer polyol. In general, tin catalysts and amine
catalysts are necessary to produce a stable foam. It
has been surprisingly discovered that when the polyol
polymer dispersions of the subject invention such as the
PIPA polymer-modified polyols are used in the polyure-
thane foam polyol component, the amount of catalyst,
particularly tin catalyst, may be lowered significantly
while still producing a stable foam, as compared with
otherwise similar formulations where polymer-modified
polyols prepared from conventionally catalyzed (basic
catalysis) base polyols are used to prepare the polymer-
modified polyol. This unexpected result allows greater
processing latitude as well as being more cost effec-
tive.
Having generally described this invention, a
further understanding can be obtained by reference to
certain specific examples which are provided herein for
purposes of illustration only and are not intended to be
limiting unless otherwise specified.
CA 02578826 2007-03-06
01-2371A -28-
Examples 1-6 and Comparative Example 1:
Double Metal Cyanide Catalyst Preparation
Example 1
Potassium hexacyanocobaltate (8.0 g) is added
to deionized water (150 mL) in a beaker, and the mixture
is blended with a homogenizer until the solids dissolve.
In a second beaker, zinc chloride (20 g) is dissolved in
deionized water (30 mL) . The aqueous zinc chloride
solution is combined with the solution of the cobalt
salt using a homogenizer to intimately mix the solu-
tions. Immediately after combining the solutions,_ a
mixture of tert-butyl alcohol (100 mL) and deionized
water (100 mL) is added slowly to the suspension of zinc
hexacyanocobaltate, and the mixture is homogenized for
10 min. The solids are isolated by centrifugation, and
are then homogenized for 10 min. with 250 mL of a 70/30
(v:v) mixture of tert-butyl alcohol and deionized water.
The solids are again isolated by centrifugation, and are
finally homogenized for 10 min. with 250 mL of tert-
butyl alcohol. The catalyst is isolated by centrifuga-
tion, and is dried in a vacuum oven at 50 C and 30 in.
(Hg) - to constant weight. The catalyst exhibits a
propylene oxide initial polymerization rate of 10.5 g
propylene oxide/min. at 105 C with a catalyst concentra-
tion of 250 ppm based on weight of product polyol,
showed no sharp lines in the X-ray diffraction (XRD)
spectrum at d-spacings of 5.07, 3.59, 2.54 and 2.28, and
had a surface area of 14 m2/g.
CA 02578826 2007-03-06
01-2371A -29-
Example 2
The procedure of Example 1 is modified as
follows. Isopropyl alcohol is substituted for tert-
butyl alcohol. Following combination of the z i nc
chloride and potassium hexacyanocobaltate solutions and
homogenization in the presence of isopropyl alcohol, the
catalyst slurry is filtered through a 0.45 micron filter
at 20 psi. The washing steps of Example 1 are also
repeated, but filtration rather than centrif::gation is
used to isolate the catalyst. The washed catalyst is
dried to constant weight as described above. The
catalyst exhibits a propylene oxide initial polymeri za-
tion rate of 1.70 g/min., and exhibited the same lack of
sharp peaks in the XRD spectrum as the catalyst of
Example 1.
Examnle 3
Potassium hexacyanocobaltate (8.0 g) is
dissolved in deionized (DI) water (140 mL) in a beaker
(Solution 1). Zinc chloride (25 g) is dissolved in DI
water (40 mL) in a second beaker (Solution 2). A t h ird
beaker contains Solution 3: a mixture of DI water (200
mL), tert-butyl alcohol (2 mL), and polyol (2 g of a
4000 mol. wt. polyoxypropylene diol prepared via double
metal cyanide catalysis.
Solutions 1 and 2 are mixed together using a
homogenizer. Immediately, a 50/50 (by volume) mixture
of tert-butyl alcohol and DI water (200 mL total) is
added to the zinc hexacyanocobaltate mixture, and the
product is homogenized for 10 min. Solution 3 (the
polyol/w4ter/tert-butyl alcohol mixture) is added to the
CA 02578826 2007-03-06
01-2371A -30-
aqueous slurry of zinc hexacyanocobaltate, and the
product is stirred -nagnetically for 3 min. The mixt u re
is filtered under pressure through a 5- m filter to
isolate the solids.
The solid cake is reslurried in tert-butyl
alcohol (140 mL) , DI water (60 mL) , and additional 4 000
mol. wt. polyoxypropylene diol (2.0 g), and the mixt u re
is homogenized for 10 min. and filtered as described
above, following which the solid cake is again
reslurried in tert-butyl alcohol (200 mL) and additional
4000 mol. wt. polyoxypropylene diol (1.0 g), homogenized
for 10 min., and filtered. The resulting solid catal yst
is dried under vacuum at 50 C (30 in. Hg) to constant
weight. The yield of dry, powdery catalyst is 10.7 g.
Elemental, thermogravimetric, and mass spec-
tral analyses of the solid catalyst show: polyol = 2 1.5
wt.%; tert-butyl alcohol = 7.0 wt.%; cobalt = 11.5 wt.%.
The catalyst exhibited a propylene oxide polymerization
rate of 3.3 Kg propylene oxide/g Co/min. and exhibited
the same lack of sharp lines in the XRD spectrum as the
catalysts of Examples 1 and 2.
Example 4
A one-gallon glass pressure reactor is charged
with a solution of potassium hexacyanocobaltate (40 g)
in DI water (700 mL) (Solution 1) . Zinc chloride
(125 g) is dissolved in a beaker with DI water (200 mL)
(Solution 2). Tert-butyl alcohol (500 mL) is dissolved
in a beaker with DI water (500 mL) (Solution 3). A
fourth mixture (Solution 4) is prepared by suspending a
4000 mol; wt. polyoxypropylene diol (60 g, same as is
CA 02578826 2007-03-06
01-2371A -31-
used in Example 3) in DI water (1000 mL) and tert-butyl
alcohol (10 mL).
Solutions 1 and 2 are combined with stirring
at 3000 rpm followed immediately by slow addition of
Solution 3 to the resulting zinc hexacyanocobaltate
mixture. The stirring rate is increased to 900 rpm, and
the mixture is stirred for 2 h at room temperature. The
stirring rate is reduced to 300 rpm, and Solution 4 is
added. The product is mixed for 5 min., and is filtered
under pressure as described in Example 1 to isolate the
solid catalyst. The solids are reslurried in tert-butyl
alcohol (700 mL) and DI water (300 mL), and stirred at
900 rpm for 2 h. The stirring rate is reduced to 300
rpm, and 60 g of the 4000 mol. wt. polyoxypropylene diol
is added. The mixture is stirred for 5 min., and is
filtered as described above.
The solids are reslurried in tert-butyl
alcohol (1000 mL) and stirred at 900 rpm for 2 h. The
stirring rate is reduced to 300 rpm, and 30 g of the
4000 mol. wt. polyoxypropylene diol is added. The
mixture is stirred for 5 min., and is filtered as
described above. The resulting solid catalyst is dried
under vacuum at 50 C (30 in. Hg) to constant weight.
The catalyst is easily crushed to a fine, dry powder.
Elemental, thermogravimetric, and mass spec-
tral analyses of the solid catalyst show: polyol = 45.8
wtA; tert-butyl alcohol = 7.4 wtA; cobalt = 6.9 wt.%.
The catalyst exhibits a propylene oxide polymerization
rate of 6.69 g propylene oxide/g Co/min., and exhibited
the same lack of sharp peaks in the XRD spectrum as the
catalysts of Examples 1-3.
CA 02578826 2007-03-06
01-2371A -32-
Example 5
The procedure of Example 1 is followed, except
that the 4000 mol. wt. polyoxypropylene diol is replaced
with a 2000 mol. wt. polyoxypropylene diol also made
using double metal cyanide catalysis.
Elemental, thermogravimetric, and mass spec-
tral analyses of the solid catalyst show: polyol = 26.5
wt.%; tert-butyl alcohol = 3.2 wt.%; cobalt = ll.-0 wt.%.
The catalyst exhibited a propylene oxide polymerization
rate of 2.34 Kg propylene oxide/g Co/min., and exhibited
the same lack of sharp peaks in the XRD spectrum as the
catalysts of Examples 1-4.
Example 6
Example 4 is repeated, except that a 4000 Da
diol end-capped with isobutylene oxide to provide c.a.
50% tertiary hydroxyl groups is used. The catalyst
exhibited higher activity than the catalyst of Example
4.
C'ompafative Example 1
This example demonstrates the preparation of
a non-encapsulative double metal cyanide complex cata-
lyst. A solution of zinc chloride (26.65 g; 0.1956 mol)
in water (26.65 g) is added rapidly to a well-agitated
solution of potassium hexacyanocobaltate (13.00 g 0.0391
mol) in water (263.35 g) . The potassium hexacyanocobal-
tate solution is maintained at 40 C during addition of
the zinc chloride solution. A white precipitate of zinc
hexacyanocobaltate particles forms immediately upon
CA 02578826 2007-03-06
01-2371A -33-
addition. After stirring for 15 minutes at 40 C,
dimethoxyethane (glyme) (84.00 g; 0.9321 mc?.) is added
to the aqueous catalyst slurry. The resulting mixture
is stirred for an additional 30 minutes and the zinc
hexacyanocobaltate=dimethoxyethane water complex cata-
lyst recovered by filtration using a horizontal basket
centrifugal filter and a light weight nylon fabric
filter medium. The filtration rate was relatively fast
with minimal clogging of the pores of the filter medium.
After washing with 300 mL dime*hoxyethane and drying in
air at ambient temperature and pressure, the filter cake
obtained is quite soft and can be easily crushed to a
fine powder.
The catalyst exhibits a propylene oxide
polymerization rate of 3.50 g propylene oxide/min.
Examples 7-1 5 and Comparative Examples 2-4
Polvoxyatkvlene Polyether Polvol Synthesis
A two-gallon stirred reactor is charged with
polyoxypropylene triol (700 mol. wt.) starter (685 g)
and zinc hexacyanocobaltate catalyst (1.63 g) . The
mixture is stirred and heated to 105'C, and is stripped
under vacuum to remove traces of water from the triol
starter. Propylene oxide (102 g) is fed to the reactor,
initially under a vacuum of 30 in. (Hg), and the reactor
pressure is monitored carefully. Additional propylene
oxide- is not added until an accelerated pressure drop
occurs in the reactor; the pressure drop is evidence
that the catalyst has become activated. When catalyst
activation is verified, the remaining propylene oxide
(5713 g) is added gradually over about 2 h while main-
taining a reactor pressure less than 40 psi. After
propylene oxide addition is complete, the mixture is
CA 02578826 2007-03-06
01-2371A -34-
held at 105'C until a constant pressure is observed.
Residual unreacted monomer is then stripped under va--aum
from the polyol product. When catalyst removal is
desired, the hot polyol product is filtered at l0O'C
through a filter cartridge (0.45 to 1.2 microns) at-
tached to the bottom of the reactor to remove the
catalyst. Residual Zn and Co are quantified by X-ray
analysis.
Polyether diols (from polypropylene glycol
starter, 450 mol. wt.) and triols are prepared as
described above using both encapsulative and non-encap-
sulative zinc hexacyanocobaltate catalysts. The poly_ol
unsaturation of the polyols produced is presented in
Table I.
TABLE I
Polyol
Example Catalyst Hydroxyl Number Unsaturation
and Functionality (meqlg)
Comparative Exam- Comparative 54 (Triol) 0.016
ples 2, 3 & 4 Example 1 27 (Triol) 0.017
15 (Triol) 0.019
Example 7 27 (Triol) 0.005
Example 8 Example 1 56 (Diol) 0.004
Example 9 27 (Diol) 0.005
Example 10 14 (Diol) 0.004
Example 11 Example 3 30 (Triol) 0.006
Example 12 Example 4 29 (Triol) 0.004
Example 13 Example 5 31 (Triol) 0.004
Example 14 Example 6 14 (Diol) 0.005
Example 15 Example 6 28 (Triol) 0.004
CA 02578826 2007-03-06
01-2371A - 35 -
Examples 16-21 and Comparative Example 5
Polymer polyols are prepared in a continuous process,
in each case employing a preformed stabilizer prepared by
capping a maleic anhydride/po.lyoxypropylene polyol half
ester with ethylene oxide and isomerizing the maleate
unsaturation to fumarate in the presence of morpholine.
The preparation of the preformed stabilizer is in
accordance with Example 1 of U.S. Patent No. 5,268,418.
A continuous polymerization system was used, employing
a tank reactor fitted with baffles and an impeller. The
feed components were pumped into the reactor continuously
after going through an inline mixer to assure complete
mixing of the feed components before entering the reactor.
The internal temperature of the reactor was controlled to
within ~ 10C at 1150C. The contents of the reactor were
well mixed. The product flowed out the top of the reactor
and into a second unagitated reactor also controlled within
1~C. The product then flowed out the top of the second
reactor continuously through a back pressure regulator
adjusted to give about 45 psig pressure on both reactors.
The crude product then flowed through a cooler into a
collection vessel. Percent by weight polymer in the
polymer polyol was determined from analysis of the amount
of unreacted monomers present in the crude product. The
crude product was vacuum stripped to remove volatiles
before testing. All of the polymer polyols were stable
compositions. In each Example, the feed rates in parts per
hour were as follows: polyol, 236.2; preformed stabilizer
25.2; catalyst (AIBN), 1.5; acrylonitrile, 60.9; styrene,
142.1.
CA 02578826 2007-03-06
01-2371A -36-
The polyols utilized were prepared in accor-
dance with the foregoing Examples. Polyoxyalkylene
content, type (triol, diol), hydroxyl numbers, catalyst
type, catalyst concentration during polyol preparation
are presented in Table II, as are the polymer solids of
the resulting polymer polyols, the initial Zn/Co concen-
trations in the polyol used to prepare the polymer
polyol, the Zn/Co concentrations in the polymer polyol
(continuous plus dispersed phases) and the Zn/Co concen-
trati,ons in the polyol (continuous) phase alone.
01-2371A -37-
TA13LE li
Base Polyol Base Polyol Base Po1yo1 Zn/Co in Base Zn/Co in Zn/Co in
Example Catalyst Type HydroxyU Composition Polyol As Used Polymer Polyol
Polyol Polymer Wt.
(Amount, ppm) Type (ppm) (ppm) Continuous Solids, %
I'hase (ppm)
Comparative Comparative 47.21Triol 10% EO 30/13 18/8 8/8 44.6
Example 5 Example 1 (125) random
16 Example 1(250) 27.1/Diol 0% EO 47/162 27/10 2/<1 44.8
17 Exaniple 3 (25) 51.8/Triol 12% EO 2/1' <11<1 <1/<I 45.1
random o
Ui
18 Example 1 (25) 51.7/Triol 12% EO 5/2 1.5/<1 <1/<1 45.8
N
random co
19 Example 1(25) 51.7rI'riol 12% EO 2.8/1.5' 2.1/1.1 <1/<1 45.3
random
0
20 Exaniplc 3 (25) 52.1/Triol 12% EO 4/2 1.7/<1 <1/<1 45.4
random
21 Example 3 (25) 56.8/Triol 12% EO 3/2 2.2/<1 <1/<1 44.9
random
' Base polyol was filtered after polyol preparation to remove a substantial
portion of catalyst residue prior to use in preparinl; polymer polyol.
= Base polyol was not filtered to remove catalyst residue, but portion of
residue had settled out. Supernatent was used for polymer polyol
preparation.
CA 02578826 2007-03-06
01-2371A -38-
As can be seen from Table II, the preparation
of polymer polyols from base polyols prepared using
prior art double metal cyanide-glyme catalyst, a non-
encapsulative double metal cyanide catalyst (Comparative
Example 5) showed little reduction in Zn/Co content in
the polymer polyol continuous phase despite starting
with a relatively low Zn/Co content for this type of
catalyzed polyol (Zn/Co = 30/13) . However, when polymer
polyols were prepared using encapsulative double metal
cyanide catalysts (Examples 16-21), in each case,
.substantial reductions of Zn/Co content, generally to
levels below the level of detection of c.a. 1 ppm, were
obtained, even in the case of high initial transition
metal content as is the case for Example 16. Such
polyols are useful in numerous applications where
polyols with higher Zn/Co content are unsuitable.
Examples 22-23: Polymer-Modifred Polyo/ Synthesis
Example 22
To 900 g of a trifunctional polyoxyalkylene
polyol having a hydroxyl number of 35, a primary
hydrbxyl content of 13 percent, and an unsaturation of
c.a. 0.0062 meq/g, prepared by the encapsulative double
metal cyanide complex catalyzed oxyalkylation of a
glycerine-initiated oligomer containing residual double
metal cyanide catalyst residues is added 48.7 g trietha-
nolamine at a temperature of c.a. 25'C. Following
thorough mixing, the agitator is turned up to high speed
and 51.7 g toluene diisocyanate is added over a period
of approximately 5 seconds under a nitrogen blanket. To
the mixture is then added 0.3 g T-12 tin catalyst
dissolved in a minor amount of additional polyol. The
temperature *rises to c.a. 40'C, following which the
CA 02578826 2007-03-06
01-2371A -39-
reaction mixture is stirred under slow speed until
cooled. The base polyol used to prepare the polymer-
modified polyol contained 6.7 ppm Zn and 2.8 ppm Co. A
white dispersion is obtained having catalyst residues
concentrated in the dispersed phase, the concentrations
of Zn and Co in the continuous polyol phase being only
0.5 ppm and < 0.2 ppm, respectively.
Example 23
The process of Example 22 is repeated, but
with the reactor charges being 1000 g polyol, 230 g
triethanolamine, and 0.03 g T-12 tin catalyst. Follow-
ing thorough mixing and heating to 54'C, the agitation
speed is increased to high and 271.0 g toluene diiso-
cyanate added over a period of 5 seconds. The tempera-
ture rapidly rises and reaches a maximum of about 105'C.
Approximately 10 seconds after isocyanate addition, 50
g DEOA-LF (diethanolamine low freezing) is added,
following which the reaction is allowed to cool with
slow agitation. A white, high solids PIPA polymer-
modified polyol dispersion is obtained with transition
metal content concentrated in the dispersed polymer
phase.
Comparative Example 6
A polymer-modified polyol was prepared as in
Example 22, using the same proportions of reactants, but
employing a conventional base-catalyzed base polyol
having a hydroxyl number of 35 and a level of unsatur-
ation of 0.027 meq/g.
CA 02578826 2007-03-06
01-2371A -40-
Examples 24-25 and Comparative Examples 7 and 8
Polyurethane Foam PreRaration
A series of all water-blown polyurethane foams
were prepared from the subject invention polymer-modi-
fied polyols synthesized in accordance with Examples 22
and 23 and a conventional polymer-modified polyol
synthesized in accordance with Comparative Example 6.
The formulations and foam quality are indicated in Table
III. below.
01-2371A -41-
TABLE III
Example 24 Example 25 Comparativc Example 7 Comparative Example 8
Polymer-Modified
Polyol From Example 22 23 C-6 C-6
Base Polyol
Unsaturation, meq/g 0.0062 0.0062 0.027' 0.027' 0
OH, % 35 35 35 35
Primary OH, % 13 13 7 7
Polymer-Modified Polyol o
Based Polyol, g 900 1000 900 900 0
Triethanolamine 48.7 230 48.7 48.7
Tolylene Diisocyanate, g 51.7 271.0 51.7 51.7
Dibutyl-tin-dilaurate, g 0.3 0.03 0.3 0.3 W
Diethanolamine (low freezing), g -- 50 -- -- o
rn
Formulation for Foam
PIPA Polynl, g 100 100 100 100
DEOA-LF, g 1.18 1.18 1.18 1.18
B-8707 silicone, g 0.5 0.5 0.5 0.5
Water, g 2.42 2.42 2.42 2.42
A-1 amine catalyst, g 0.11 0.11 0.11 0.11
T-12 tin catalyst, g 0.07 0.07 0.07 0.25
TDI, g 39 39 39 39
Foam Appearance Good Good Collapses Very Porous
Conventional base-catalyzed base polyol.
CA 02578826 2007-03-06
01-2371A -42-
As can be seen, both the polymer-modified
polyols of the suhject invention (from Examples 22 and
23) employing low-unsaturation base polyols, foamed well
at 0.07 parts tin catalyst per 100 parts polyol, while
polymer-modified polyols prepared from conventionally
catalyzed base polyols (from Comparative Example 6) did
not produce a stable foam at the same catalyst concen-
tration, the foam exhibiting collapse, and produced only
a poor quality, very porous foam even at a tin catalyst
level higher by a factor of almost four. These resulto
are totally unexpected.
Having now fully described the invention, it
will be apparent to one of ordinary skill in the art
that many changes and modifications can be made thereto
without departing from the spirit or scope of the
invention as set forth herein.
