Highly active double metal cyanide catalysts

Improved double metal cyanide (DMC) catalysts are disclosed. The catalysts comprise a DMC compound, an organic complexing agent, from about 0.1 to about 10 wt. % of an organophosphine oxide, and optionally, a polyether. Compared with other DMC catalysts prepared in the absence of the organophosphine oxide, those of the invention have higher activity for epoxide polymerization, and they give polyols having reduced unsaturation even at high epoxide polymerization temperatures.

FIELD OF THE INVENTION 
The invention relates to double metal cyanide (DMC) catalysts useful for 
epoxide polymerization. In particular, the invention relates to DMC 
catalysts that have high activity and that give very low unsaturation 
polyols even at relatively high epoxide polymerization temperatures. 
BACKGROUND OF THE INVENTION 
Double metal cyanide complexes are well-known catalysts for epoxide 
polymerization. These active catalysts give polyether polyols that have 
low unsaturation compared with similar polyols made using basic (KOH) 
catalysis. The catalysts can be used to make many polymer products, 
including polyether, polyester, and polyetherester polyols. The polyols 
can be used in polyurethane coatings, elastomers, sealants, foams, and 
adhesives. 
DMC catalysts are usually made by reacting aqueous solutions of metal salts 
and metal cyanide salts to form a precipitate of the DMC compound. A low 
molecular weight organic complexing agent, typically an ether or an 
alcohol is included in the catalyst preparation. The organic complexing 
agent is needed for favorable catalyst activity. Preparation of typical 
DMC catalysts is described, for example, in U.S. Pat. Nos. 3,427,256, 
3,829,505, and 5,158,922. 
We recently described substantially amorphous DMC catalysts that have 
exceptional activity for polymerizing epoxides (see U.S. Pat. No. 
5,470,813). We also described highly active DMC catalysts that include, in 
addition to a low molecular weight organic complexing agent, from about 5 
to about 80 wt. % of a polyether such as a polyoxypropylene polyol (see 
U.S. Pat. No. 5,482,908). Compared with earlier DMC catalysts, the DMC 
catalysts described in U.S. Pat. Nos. 5,470,813 and 5,482,908 have 
excellent activity and give polyether polyols with very low unsaturation. 
The catalysts are active enough to allow their use at very low 
concentrations, often low enough to overcome any need to remove the 
catalyst from the polyol. Catalysts with even higher activity are 
desirable because reduced catalyst levels could be used. 
One drawback of DMC catalysts now known is that polyol unsaturations 
increase with epoxide polymerization temperature. Thus, polyols prepared 
at higher reaction temperatures (usually to achieve higher reaction rates) 
tend to have increased unsaturation levels. This sensitivity of 
unsaturation to increases in epoxide polymerization temperature is 
preferably minimized or eliminated. 
Matsumoto et al. (Jap. Pat. Appl. Kokai No. H6-184297) teach to use an 
organophosphine oxide as a cocatalyst in a KOH-catalyzed epoxide 
polymerization to enable increased reaction rates without an increase in 
polyol unsaturation. The use of the organophosphine oxide is only taught 
in connection with alkali metal and alkaline earth metal (basic) 
catalysts; the reference is silent regarding the potential impact of using 
an organophosphine oxide with a coordination catalyst such as a double 
metal cyanide catalyst. 
An ideal catalyst would give polyether polyols with low unsaturation and 
would be active enough to use at very low concentrations, preferably at 
concentrations low enough to overcome any need to remove the catalyst from 
the polyol. Particularly valuable would be a catalyst that can produce 
polyether polyols having very low unsaturation levels over a broad range 
of epoxide polymerization temperatures. 
SUMMARY OF THE INVENTION 
The invention is a double metal cyanide (DMC) catalyst useful for epoxide 
polymerizations. The catalyst comprises a DMC compound, an organic 
complexing agent, an organophosphine oxide, and optionally, a polyether. 
The catalyst contains from about 0.1 to about 10 wt. % of the 
organophosphine oxide. When a polyether is included, the catalyst contains 
from about 5 to about 80 wt. % of the polyether. The invention also 
includes a method for making the catalysts, and processes for making 
epoxide polymers. 
I surprisingly found that DMC catalysts that include an organophosphine 
oxide have improved activities compared with similar catalysts made in the 
absence of the organophosphine oxide. In addition, the catalysts of the 
invention give polyols having very low unsaturations even at relatively 
high epoxide polymerization temperatures. The reduced sensitivity of 
unsaturation to reaction temperature allows for efficient production of 
polyether polyols while maintaining high product quality.

DETAILED DESCRIPTION OF THE INVENTION 
Catalysts of the invention comprise a double metal cyanide (DMC) compound, 
an organic complexing agent, an organophosphine oxide, and optionally, a 
polyether. 
Double metal cyanide compounds useful in the invention are the reaction 
products of a water-soluble metal salt and a water-soluble metal cyanide 
salt. The water-soluble metal salt preferably has the general formula 
M(X).sub.n in which M is selected from the group consisting of Zn(II), 
Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), 
AI(III), V(V), V(IV), Sr(II), W(IV), W(VI), Cu(II), and Cr(III). More 
preferably, M is selected from the group consisting of Zn(II), Fe(II), 
Co(II), and Ni(II). In the formula, X is preferably an anion selected from 
the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, 
oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and 
nitrate. The value of n is from 1 to 3 and satisfies the valency state of 
M. Examples of suitable metal salts include, but are not limited to, zinc 
chloride, zinc bromide, zinc acetate, zinc acetonylacetate, zinc benzoate, 
zinc nitrate, iron(II) sulfate, iron(II) bromide, cobalt(II) chloride, 
cobalt(II) thiocyanate, nickel(II) formate, nickel(II) nitrate, and the 
like, and mixtures thereof. 
The water-soluble metal cyanide salts used to make the double metal cyanide 
compounds useful in the invention preferably have the general formula 
(Y).sub.a M'(CN).sub.b (A).sub.c in which M' is selected from the group 
consisting of Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), 
Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV), and V(V). More 
preferably, M' is selected from the group consisting of Co(II), Co(III), 
Fe(II), Fe(III), Cr(III), Ir(III), and Ni(II). The water-soluble metal 
cyanide salt can contain one or more of these metals. In the formula, Y is 
an alkali metal ion or alkaline earth metal ion. A is an anion selected 
from the group consisting of halide, hydroxide, sulfate, carbonate, 
cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, 
and nitrate. Both a and b are integers greater than or equal to 1; the sum 
of the charges of a, b, and c balances the charge of M'. Suitable 
water-soluble metal cyanide salts include, but are not limited to, 
potassium hexacyanocobaltate(III), potassium hexacyanoferrate(II), 
potassium hexacyanoferrate(III), calcium hexacyanocobaltate(III), lithium 
hexacyanoiridate(III), and the like. 
Examples of double metal cyanide compounds that can be used in the 
invention include, for example, zinc hexacyanocobaltate(III), zinc 
hexacyanoferrate(III), zinc hexacyanoferrate(II), nickel(II) 
hexacyanoferrate(II), cobalt(II) hexacyanocobaltate(III), and the like. 
Further examples of suitable double metal cyanide compounds are listed in 
U.S. Pat. No. 5,158,922, the teachings of which are incorporated herein by 
reference. 
The DMC catalysts of the invention include an organic complexing agent. 
Generally, the complexing agent must be relatively soluble in water. 
Suitable complexing agents are those commonly known in the art, as taught, 
for example, in U.S. Pat. No. 5,158,922. The complexing agent is added 
either during preparation or immediately following precipitation of the 
catalyst. Usually, an excess amount of the complexing agent is used. 
Preferred complexing agents are water-soluble heteroatom-containing 
organic compounds that can complex with the double metal cyanide compound. 
Suitable complexing agents include, but are not limited to, alcohols, 
aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides, and 
mixtures thereof. Preferred complexing agents are water-soluble aliphatic 
alcohols selected from the group consisting of ethanol, isopropyl alcohol, 
n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, and tert-butyl 
alcohol. Tert-butyl alcohol is most preferred. 
A key component of the DMC catalysts of the invention is an organophosphine 
oxide. Suitable organophosphine oxides have one or more C.sub.1 -C.sub.30 
aryl, alkyl, or aralkyl groups attached to phosphorus. Preferred 
organophosphine oxides have the general formula R.sub.3 P.dbd.O in which R 
is a C.sub.1 -C.sub.20 alkyl group. Suitable organophosphine oxides 
include, for example, tri-n-methylphosphine oxide, tri-n-butylphosphine 
oxide, tri-n-octylphosphine oxide, triphenylphosphine oxide, 
methyldibenzylphosphine oxide, and the like, and mixtures thereof. The 
organophosphine oxide is present in the catalyst in an amount within the 
range of about 0.1 to about 10 wt. %; a more preferred range is from about 
0.5 to about 5 wt. %. 
I surprisingly found that catalysts prepared in the presence of an 
organophosphine oxide have high activity for polymerizing epoxides, and 
they can be used to make polyols having very low unsaturations even at 
relatively high epoxide polymerization temperatures. The examples below 
demonstrate the advantage of incorporating an organophosphine oxide into 
the DMC catalyst. 
As the results in Tables 1-2 show, incorporating an organophosphine oxide 
into a DMC catalyst makes the catalyst activate more quickly and 
polymerize propylene oxide at a faster rate. In addition, polyols made 
from the catalysts of the invention have reduced unsaturation levels. As 
Table 3 shows, the benefit is also obtained when the organophosphine oxide 
is not part of the DMC catalyst, but is simply added to the reaction 
mixture during the epoxide polymerization. 
The DMC catalysts of the invention optionally include from about 5 to about 
80 wt. % of a polyether, which is preferably a polyether polyol. 
Preferably, the catalysts include from about 10 to about 70 wt. %, and 
more preferably from about 15 to about 60 wt. % of the polyether. At least 
about 5 wt. % of the polyether is needed to significantly improve the 
catalyst activity compared with a catalyst made in the absence of the 
polyether polyol. Catalysts that contain more than about 80 wt. % of the 
polyether polyol are generally no more active, and they are impractical to 
isolate and use because they are typically sticky pastes rather than 
powdery solids. 
Suitable polyethers include those produced by ring-opening polymerization 
of cyclic ethers, and include epoxide polymers, oxetane polymers, 
tetrahydrofuran polymers, and the like. Any method of catalysis (acid, 
base, or coordination catalyst) can be used to make the polyethers. The 
polyethers can have any desired end groups, including, for example, 
hydroxyl, amine, ester, ether, or the like. Preferred polyethers are 
polyether polyols having average hydroxyl functionalities from about 2 to 
about 8 and number average molecular weights within the range of about 200 
to about 10,000, more preferably from about 1000 to about 5000. Polyols 
having at least about 5%, and preferably at least about 20% of tertiary 
hydroxyl end groups, are particularly preferred. The polyols are usually 
made by polymerizing epoxides in the presence of active 
hydrogen-containing initiators and basic, acidic, or organometallic 
catalysts (including DMC catalysts). Useful polyether polyols include 
poly(oxypropylene) polyols, EO-capped poly(oxypropylene) polyols, mixed 
EO-PO polyols, butylene oxide polymers, butylene oxide copolymers with 
ethylene oxide and/or propylene oxide, polytetramethylene ether glycols, 
and the like. Most preferred are poly(oxypropylene) polyols and 
isobutylene oxide-capped poly(oxypropylene) polyols having number average 
molecular weights within the range of about 200 to about 4000. 
The invention includes a method for making the catalysts. The method 
comprises reacting aqueous solutions of a metal salt and a metal cyanide 
salt in the presence of an organic complexing agent, an organophosphine 
oxide, and optionally, a polyether to produce a DMC catalyst that contains 
from about 0.1 to about 10 wt. % of the organophosphine oxide. 
In a typical method, aqueous solutions of a metal salt (such as zinc 
chloride) and a metal cyanide salt (such as potassium hexacyanocobaltate) 
are first reacted in the presence of an organophosphine oxide and an 
organic complexing agent (such as tert-butyl alcohol) using efficient 
mixing to produce a catalyst slurry. The metal salt is used in excess. The 
catalyst slurry contains the reaction product of the metal salt and metal 
cyanide salt, which is the double metal cyanide compound. Also present are 
excess metal salt, water, organophosphine oxide, and organic complexing 
agent; each is incorporated to some extent in the catalyst structure. 
The organic complexing agent and organophosphine oxide can be included with 
either or both of the aqueous salt solutions, or they can be added to the 
catalyst slurry immediately following precipitation of the DMC compound. 
It is generally preferred to pre-mix the complexing agent and 
organophosphine oxide with either aqueous solution, or both, before 
combining the reactants. If the complexing agent is added to the catalyst 
precipitate instead, then the reaction mixture should be mixed efficiently 
with a homogenizer or a high-shear stirrer to produce the most active form 
of the catalyst. 
The catalyst slurry produced as described above is optionally combined with 
a polyether, preferably a polyether polyol. This is preferably done using 
low-shear mixing to avoid thickening or coagulation of the reaction 
mixture. The polyether-containing catalyst is then usually isolated from 
the catalyst slurry by any convenient means, such as filtration, 
centrifugation, decanting, or the like. 
The isolated polyether-containing solid catalyst is preferably washed with 
an aqueous solution that contains additional organic complexing agent. 
After the catalyst has been washed, it is usually preferred to dry it 
under vacuum until the catalyst reaches a constant weight. Suitable 
techniques for washing and isolating the catalyst are described in U.S. 
Pat. No. 5,482,908, the teachings of which are incorporated herein by 
reference. 
The invention includes a process for making an epoxide polymer. This 
process comprises polymerizing an epoxide in the presence of a double 
metal cyanide catalyst of the invention. Preferred epoxides are ethylene 
oxide, propylene oxide, butene oxides, styrene oxide, and the like, and 
mixtures thereof. The process can be used to make random or block 
copolymers. The epoxide polymer can be, for example, a polyether polyol 
derived from the polymerization of an epoxide in the presence of a 
hydroxyl group-containing initiator. 
Other monomers that will copolymerize with an epoxide in the presence of a 
DMC compound can be included in the process of the invention to make other 
types of epoxide polymers. Any of the copolymers known in the art made 
using conventional DMC catalysts can be made with the catalysts of the 
invention. For example, epoxides copolymerize with oxetanes (as taught in 
U.S. Pat. Nos. 3,278,457 and 3,404,109) to give polyethers, or with 
anhydrides (as taught in U.S. Pat. Nos. 5,145,883 and 3,538,043) to give 
polyester or polyetherester polyols. The preparation of polyether, 
polyester, and polyetherester polyols using double metal cyanide catalysts 
is fully described, for example, in U.S. Pat. Nos. 5,223,583, 5,145,883, 
4,472,560, 3,941,849, 3,900,518, 3,538,043, 3,404,109, 3,278,458, 
3,278,457, and in J. L. Schuchardt and S. D. Harper, SPI Proceedings, 32nd 
Annual Polyurethane Tech./Market. Conf. (1989) 360. The teachings of these 
U.S. patents related to polyol synthesis using DMC catalysts are 
incorporated herein by reference in their entirety. 
Polyether polyols made with the catalysts of the invention preferably have 
average hydroxyl functionalities from about 2 to 8, more preferably from 
about 2 to 6, and most preferably from about 2 to 3. The polyols 
preferably have number average molecular weights within the range of about 
500 to about 50,000. A more preferred range is from about 1,000 to about 
12,000; most preferred is the range from about 2,000 to about 8,000. 
The following examples merely illustrate the invention. Those skilled in 
the art will recognize many variations that are within the spirit of the 
invention and scope of the claims. 
EXAMPLE 1 
Preparation of a DMC Catalyst Containing Tri-n-octylphosphine Oxide 
Zinc chloride (75 g) and tri-n-octylphosphine oxide (0.375 g) are dissolved 
in a beaker with a mixture of tert-butyl alcohol (50 mL) and distilled 
water (275 mL) (Solution 1 ). Solution 2 is prepared by dissolving 
potassium hexacyanocobaltate (7.5 g) in distilled water (100 mL). Solution 
3 contains tert-butyl alcohol (2.0 mL) and distilled water (200 mL). 
Solutions 1 and 2 are mixed together in a beaker using a homogenizer at 20% 
of maximum intensity. The mixing rate is increased to 40% intensity for 10 
min. Solution 3 is added to the aqueous zinc hexacyanocobaltate slurry, 
and the mixture is stirred magnetically for 3 min. Catalyst solids are 
isolated by centrifugation. 
The catalyst solids are reslurried in a mixture of tert-butyl alcohol (130 
mL) and distilled water (55 mL) and homogenized for 10 min. at 40% 
intensity, and are then isolated as described above. The solids are 
reslurried in tert-butyl alcohol (185 mL) containing dissolved 
tri-n-octylphosphine oxide (0.375 g), and are homogenized at 40% intensity 
for 10 min. The solids are isolated by centrifugation, and are dried at 
60.degree. C. (30 in. Hg) to constant weight. The yield of dry, powdery 
catalyst is 7.2 g. By elemental analysis, the catalyst contains 12.6 wt. % 
Co and 26.2 wt. % Zn. 
COMATIVE EXAMPLE 2 
The procedure of Example 1 is followed, except that tri-n-octylphosphine 
oxide is omitted. The yield of dry, powdery catalyst is 6.5 g. By 
elemental analysis, the catalyst contains 13.8 wt. % Co and 30.2 wt. % Zn. 
EXAMPLE 3 
Preparation of a DMC Catalyst Containing Tri-n-octylphosphine Oxide and a 
Polyoxypropylene Diol (PPG-425 diol) 
Zinc chloride (75 g) and tri-n-octylphosphine oxide (0.375 g) are dissolved 
in a beaker with a mixture of tert-butyl alcohol (50 mL) and distilled 
water (275 mL) (Solution 1 ). Solution 2 is prepared by dissolving 
potassium hexacyanocobaltate (7.5 g) in distilled water (100 mL). Solution 
3 contains tertbutyl alcohol (2.0 mL), PPG-425 diol (400 mol. wt. 
poly(oxypropylene) diol, 4.0 g) and distilled water (200 mL). 
Solutions 1 and 2 are mixed together in a beaker using a homogenizer at 20% 
of maximum intensity. The mixing rate is increased to 40% intensity for 10 
min. Solution 3 is added to the aqueous zinc hexacyanocobaltate slurry, 
and the mixture is stirred magnetically for 3 min. Catalyst solids are 
isolated by filtering the mixture through 5.0 micron filter paper at 40 
psig. 
The catalyst solids are reslurried in a mixture of tert-butyl alcohol (130 
mL) and distilled water (55 mL) and homogenized for 10 min. at 40% 
intensity. Additional PPG-425 diol (1.0 g) is added, and the mixture is 
magnetically stirred for 3 min. The catalyst solids are then isolated by 
filtration as described above. The solids are reslurried in tert-butyl 
alcohol (185 mL) containing dissolved tri-n-octylphosphine oxide (0.375 
g), and are homogenized at 40% intensity for 10 min. Additional PPG-425 
diol (1.0 g) is added, and the mixture is stirred for 3 min. The solids 
are isolated by filtration, and are dried at 60.degree. C. (30 in. Hg) to 
constant weight. The yield of dry, powdery catalyst is 10.3 g. 
COMATIVE EXAMPLE 4 
Preparation of a DMC Catalyst Containing a Polyoxypropylene Diol, but no 
Tri-n-octylphosphine Oxide 
The procedure of Example 3 is followed, except that tri-n-octylphosphine 
oxide is omitted from the formulation. The yield of dry, powdery catalyst 
is 9.3 g. 
EXAMPLE 5 
Measurement of Catalyst Activity 
Activities of the catalysts of Example 1 and Comparative Example 2 are 
measured during the preparation of polyether triols (hydroxyl number=30 mg 
KOH/g) as follows. 
A one-liter stirred reactor is charged with 70 g of a 700 mol. wt. 
poly(oxypropylene) triol starter polyol and zinc 
hexacyanocobaltate/tert-butyl alcohol catalyst (0.029 g) (50 ppm of 
catalyst in the final polyol product). The mixture is stirred and heated 
to 105.degree. C. under vacuum to remove traces of residual water. 
Propylene oxide (PO) (10 g) is added to the reactor, and the pressure in 
the reactor is increased from vacuum to about 4 psig. An accelerated drop 
in reactor pressure soon occurs, indicating that the catalyst has become 
activated. After initiation of the catalyst is verified, additional 
propylene oxide (a total of 500 g) is added slowly to the reactor to 
maintain the reactor pressure at about 10 psig. 
Catalyst activity is measured from the slope of a PO conversion vs. time 
plot at its steepest point, and is reported in terms of kg PO per gram of 
cobalt per minute (see Table 1). After the PO addition is complete, the 
reaction mixture is held at 105.degree. C. until a constant pressure is 
obtained, which indicates that PO conversion is complete. The mixture is 
vacuum stripped at 60.degree. C. for 0.5 h to remove any traces of 
unreacted PO from the reactor. The product is cooled and recovered. The 
product is a poly(oxypropylene) triol having a hydroxyl number of about 30 
mg KOH/g. 
As the results in Table 1 show, catalyst activity increases from 4.6 to 5.6 
kg PO/g Co/min. when tri-n-octylphosphine oxide is incorporated into the 
catalyst. 
EXAMPLE 6 
Polyether Polyol Synthesis: Preparation of an 8K Mol. Wt. Polyoxypropylene 
Diol 
The catalysts of Example 3 and Comparative Example 4 are used to make 8000 
molecular weight polyoxypropylene diols as described below. 
A one-liter stirred reactor is charged with polyoxypropylene diol (1000 
mol. wt.) starter (77 g) and zinc hexacyanocobaltate/tert butyl 
alcohol/PPG-425 diol catalyst (0.015 g, 25 ppm based on the amount of 
finished polyol product). The mixture is stirred and heated to 105.degree. 
C., and is stripped under vacuum for 0.5 h to remove traces of water from 
the diol starter. After stripping, the reaction temperature is raised to 
145.degree. C. Propylene oxide (12 g) is fed to the reactor, initially 
under a vacuum of about 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 (512 g) is added gradually over about 4 h. 
After propylene oxide addition is complete, the mixture is held at 
145.degree. C. until a constant pressure is observed. Residual unreacted 
monomer is then stripped under vacuum at 60.degree. C. from the polyol 
product. The warm polyol product is filtered through a filter cartridge 
(0.45 to 1.2 microns) attached to the bottom of the reactor to remove the 
catalyst. Polyol unsaturations are compared in Table 2. 
The results in Table 2 show that an 8K mol. wt. diol prepared with a DMC 
catalyst that incorporates an organophosphine oxide has reduced 
unsaturation compared with a diol made with a catalyst that does not 
contain the organophosphine oxide. Unsaturation drops from 0.0154 to 
0.0108 meq/g. 
EXAMPLES 7-8 and COMATIVE EXAMPLE 9 
Effect of Adding the Organophosphine Oxide to the Reaction Mixture in the 
Preparation of an 8K Mol. Wt. Polyoxypropylene Diol 
The procedure of Example 6 is generally followed to make an 8000 molecular 
weight polyoxypropylene diol with the zinc hexacyanocobaltate/tert-butyl 
alcohol catalyst of Comparative Example 2. In Examples 7 and 8, 
tri-n-octylphosphine oxide (25 ppm or 100 ppm) is added to the 
polymerization mixture. In Comparative Example 9, the organophosphine 
oxide is omitted. Table 3 summarizes the polyol unsaturation results. 
As Table 3 shows, the unsaturation of polyether polyols made using DMC 
catalysts can be reduced simply by adding a small amount of an 
organophosphine oxide to the reaction mixture. Addition of 25 ppm of 
tri-n-octylphosphine oxide reduces unsaturation of an 8000 molecular 
weight polyoxypropylene diol from 0.009 to 0.007 meq/g. 
The preceding examples are meant only as illustrations. The scope of the 
invention is defined by the claims. 
TABLE 1 
__________________________________________________________________________ 
Effect of Organophosphine Oxide on Activity of DMC Catalysts 
Activation time 
Activity (kg PO/g 
Catalyst of Ex # 
Catalyst 
Level (ppm) 
Temp. (.degree.C.) 
(min) Co/min) 
__________________________________________________________________________ 
1 Zn--Co/TBA/ 
50 105 162 5.6 
TOPO 
C2 Zn--Co/TBA 
50 105 220 4.6 
__________________________________________________________________________ 
Zn--Co/TBA = zinc hexacyanocobaltate/tertbutyl alcohol complex; TOPO = 
trin-octylphosphine oxide 
Catalyst level is based on the amount of polyol product made. 
C = comparative example 
TABLE 2 
______________________________________ 
Effect of Organophosphine Oxide on Polyol Unsaturation 
Catalyst Level 8K Diol Unsaturation 
of Ex # 
Catalyst (ppm) Temp. (.degree.C.) 
(meq/g) 
______________________________________ 
3 Zn--Co/TBA/ 
25 145 0.0108 
PPG-425/ 
TOPO 
C4 Zn--Co/TBA/ 
25 145 0.0154 
PPG-425 
______________________________________ 
Zn--Co/TBA = zinc hexacyanocobaltate/tertbutyl alcohol complex; TOPO = 
trin-octylphosphine oxide 
Catalyst level is based on the amount of polyol product made. 
C = comparative example 
TABLE 3 
______________________________________ 
Effect of Adding Organophosphine Oxide during Polymerization on Polyol 
Unsaturation 
TOPO added 
Temp. 8K Diol Unsaturation 
Ex # Catalyst (ppm) (.degree.C.) 
(meq/g) 
______________________________________ 
7 Zn--Co/TBA 25 145 0.0070 
8 Zn--Co/TBA 100 145 0.0072 
C9 Zn--Co/TBA 0 145 0.0090 
______________________________________ 
Zn--Co/TBA = zinc hexacyanocobaltate/tertbutyl alcohol complex (prepared 
as in Comparative Example 2). 
TOPO = trin-octylphosphine oxide 
C = comparative example