Polymer/polyol and preformed stabilizer systems

Improved polymer/polyol compositions and processes for making them; high potency preformed stabilizers used to make the polymer/polyol compositions and processes for making them; and improved polyurethane products made from the polymer/polyols compositions; characterized by a material reduction in polymer/polyol viscosity while raising the polymer solids content.

BRIEF DESCRIPTION OF THE INVENTION 
The present invention relates to: improved polymer/polyol compositions and 
processes for making them; high potency preformed stabilizers used to make 
the polymer/polyol compositions and processes for making them; and 
improved polyurethane products made from the polymer/polyols compositions. 
BRIEF BACKGROUND TO THE INVENTION 
Seymour, Polymers for Engineering Applications, ASM International (1987), 
Gowariker et al., Polymer Science, John Wiley & Sons Inc. (1986) and 
Barrett (Ed.), Dispersion Polymerization in Organic Media, John Wiley & 
Sons Inc. (1975) are recommended background reading material. 
Polymer/polyol compositions suitable for use in producing polyurethane 
foams, elastomers and the like, and the polyurethanes, are commercial 
products. The two major types of these polyurethane foams are termed 
slabstock and molded. Slabstock foams are used in the carpet, furniture 
and bedding industries. Primary uses of slabstock foam are as carpet 
underlay and furniture padding. In the molded foam area, high resiliency 
(HR) molded foam is the foam type generally made. HR molded foams are used 
in the automotive industry for a breadth of applications ranging from 
molded seats to energy-absorbing padding and the like. 
The basic patents relating to such polymer/polyol compositions are 
Stamberger U.S. Pat. No. Re. 28,715 (reissue of U.S. Pat. No. 3,383,351) 
and U.S. Pat. No. Re. 29,118 (reissue of U.S. Pat. No. 3,304,273). A 
stable dispersion of polymer particles in a polyol can be produced by 
polymerizing one or more ethylenically unsaturated monomer dissolved or 
dispersed in a polyol in the presence of a free radical catalyst. These 
polymer/polyol compositions produce polyurethane foams and elastomers 
having higher load-bearing capacities than those produced from unmodified 
polyols. 
Initially, the primary polymer/polyol compositions accepted commercially 
used acrylonitrile in its manufacture. Many of these compositions 
possessed undesirably high viscosities for certain applications. More 
recently, acrylonitrile-styrene monomer mixtures have been used 
commercially to make the polymer component of polymer/polyols. 
The expanding demand for polymer/polyols has highlighted several product 
needs and this has spawned additional advances in technology. For example, 
a market demand has evolved for "virtually" scorch-free slabstock foams, 
i.e., white foam products. Virtually scorch-free foams possessing 
satisfactory load-bearing and other foam properties, even at 
ever-decreasing densities (viz.-1.5 pounds per cubic foot or less), are 
available without substantial economic penalty. 
Virtually scorch-free foams are achieved by using relatively high styrene 
contents (e.g., about 65 to 70 percent styrene) in the 
acrylonitrile-styrene monomer mixture. In addition, such high styrene 
monomer mixtures are used broadly in the molded foam area. 
Still, polymer/polyols derived from such high styrene monomer mixtures 
appear incapable of satisfying ever-increasing market needs, which include 
rigorous stability requirements and increased load-bearing 
characteristics. This is particularly prevalent in the slabstock area 
where many formulations require the use of "neat" polymer/polyols, i.e., 
polymer/polyol undiluted by conventional polyols. Though neat 
polymer/polyols are not usually employed in the molded foam area, there is 
a need for polymer/polyols which can impart higher load-bearing 
characteristics to such foams. 
Polymer/polyols with increased load-bearing characteristics can be obtained 
by increasing their polymer or solid contents. Solid contents of 30 to 60 
weight percent, or higher, are desired. Yet, the art has not been capable 
of increasing solid contents without reducing the stability of the 
polymer/polyol and undesirably increasing its viscosity. 
Employment of high styrene monomer mixtures and high solid contents' 
polymer/polyols, by prior practices, generally resulted in undesirably 
high viscosity polymer/polyols. The viscosity of a polymer/polyol should 
be sufficiently low for ease of handling during its manufacture. In 
addition, the viscosity should facilitate transport, handling and, 
ultimately, adequate processability, in the employed foam processing 
equipment. Because of increased usage of sophisticated mixing systems, 
such as impingement systems, excessive viscosity of the polymer/polyol is 
becoming a significant problem in the molded area. The need for lower 
viscosity polymer/polyols is apparent to satisfy these increased demands 
in the art. 
As indicated, polymer/polyol stability is a concern to makers of 
polyurethanes. Once, seediness or filterability, a measure of stability of 
polymer/polyols, was not a major issue in commercial practices. With 
advances in the state of the art of polyurethane production, 
polymer/polylol stability criteria were revised, especially in the molded 
foam area. 
With commecial developments in sophisticated, high-speed and large-volume 
equipment and systems for handling, mixing and reacting 
polyurethane-forming ingredients have evolved the need for highly stable 
and low viscosity polymer/polyols. Polymer/polyols have certain minimum 
requirements for satisfactory processing in such sophisticated foam 
equipment. Typically, the prime requirement is that the polymer/polyols 
possess sufficiently small particles so that filters, pumps and the like 
do not become plugged or fouled in relatively short periods of time. 
Though there have been advances in reduction in viscosity and increase in 
solids of polymer/polyols, there is a need for improvement in viscosity 
reduction and increase in solids content. Greater reductions in viscosity 
are needed to meet market demands and greater effective increases in 
solids content are also needed by the market. More importantly, there is a 
need for technology in polymer/polyol that maximizes viscosity reduction 
while also providing a viable mechanism to higher solids content. 
Priest et al., U.S. Pat. No. 4,208,314 describe low viscosity 
polymer/polyols made from acrylonitrile-styrene monomer mixtures. These 
polymer/polyols are convertible to low density, water-blown polyurethane 
foams having reduced scorch, especially with relatively low 
acrylonitrile-to-styrene ratios. The Priest et al. patent also provides a 
process for making polymer/polyols with reduced particulates. 
Enhanced stability of polymer/polyols is believed to be provided by the 
presence of a minor amount of a graft or addition copolymer formed in situ 
from growing polymer chains and polyol molecules. Some prior approaches 
incorporate small amounts of unsaturation into the polyol in addition to 
that inherently present in the polyoxyalkylene polyols typically used in 
forming polymer/polyols. This was done in the belief that improved 
stability will result due to an increased amount of an addition copolymer 
stabilizer expected to be formed. U.S. Pat. Nos. 3,652,639, 3,823,201, and 
3,850,861, British Patent No. 1,126,025 and Japanese Patent Nos. 52-80919 
and 48,101494 utilize this approach. This use of "stabilizer precursors," 
also termed a "macromer" that contains a particular level of reactive 
unsaturation, is based on the belief that during polymerization, in the 
preparation of the polymer/polyol, adequate amounts of stabilizer will be 
formed by the addition polymerization of the precursor stabilizer with a 
growing polymer chain. 
The general concept of using stabilizer precursors in polymerization is 
discussed in Barrett (1975), supra. U.S. Pat. Nos. 4,454,255 and 4,458,038 
illustrate this technique. The macromer in the '255 and '038 patents may 
be obtained by reacting a polyol with a compound having reactive ethylenic 
unsaturation such as, for example, maleic anhydride or fumaric acid. A 
further example of the use of this technique is U.S. Pat. No. 4,460,715. 
The reactive unsaturation in the '715 stabilizer is provided by an 
acrylate or methacrylate moiety. 
Van Cleve et al., U.S. Pat. No. 4,242,249 disclose improved polymer/polyols 
prepared by utilizing certain preformed dispersants or stabilizers. These 
polymer/polyols provide stability satisfactory for commercial production, 
and use of one or more of the following: (1) higher amounts of styrene or 
other comonomer when acrylonitrile copolymer polymer/polyols are being 
prepared, (2) higher polymer contents or (3) the use of lower molecular 
weight polyols. The particular dispersant employed and the concentration 
utilized vary with respect to the monomer system used in preparing the 
polymer/polyols. 
U.S. Pat. No. 4,550,194 prepares a polyol by reacting a conventional 
polyether polyol with an organic compound having ethylenic unsaturation 
and an anhydride group forming a half ester and subsequently reacting that 
product with alkylene oxide in the presence of calcium naphthenate or 
cobalt naphthenate. Example 51 of the patent uses pentaerythritol. 
Simroth et al., U.S. Pat. No. 4,652,589, patented Mar. 24, 1987, describe 
stabilizer precursors for polymer/polyols. Stabilizer A is made by 
reacting a 34 hydroxyl number, 15 weight percent ethylene oxide capped 
polyoxyproxylene triol with maleic anhydride and subsequently with 
ethylene oxide. The stabilizer precursor has a hydroxyl number of 32, an 
unsaturation of 0.1 meq/gm, with the unsaturation being 30/70 
maleate/fumarate. The retained unsaturation is 50 percent of the 
unsaturation provided by the maleic anhydride. Stabilizer B is made by 
reacting a 28 hydroxyl number sorbitol started polyol, containing 10% 
internal ethylene oxide, with maleic anhydride, and subsequently with 
propylene oxide. The precursor stabilizer has a hydroxyl number of 28 and 
an unsaturation of approximately 0.07 meq/g, with the unsaturation being 
of the fumarate type. The retained unsaturation is 70 percent of the 
unsaturation provided by the maleic anhydride. 
European Patent Application 87114233.7 based on copending U.S. application 
Ser. No. 913,328, filed Sep. 30, 1986, now U.S. Pat. No. 4,997,857 is 
directed to stabilizers having four key features: (1) they are prepared 
from a starting polyol having a functionality greater than 4; (2) they 
have at least 60% retained unsaturation; (3) they have viscosities greater 
than 2000 centipoises at 25.degree. C.; and (4) the starting polyol is 
capped with ethylene oxide and/or the adduct formed between the starting 
polyol and the a reactive unsaturated compound is capped with ethylene 
oxide. 
Other prior art of interest include Simroth et al., U.S. Pat. No. Re. 
32,733, patented Aug. 16, 1988, Ramlow et al., U.S. Pat. No. 3,931,092, 
patented Jan. 6, 1976, Ramlow et al., U.S. Pat. No. 4,014,846, patented 
Mar. 29, 1977, Ramlow et al., U.S. Pat. No. 4,093,573, patented Jun. 6, 
1978, Shah, U.S. Pat. No. 4,148,840, patented Apr. 10, 1979, Shook et al., 
U.S. Pat. No. 4,172,825, patented Oct. 30, 1979, Kozawa et al., U.S. Pat. 
No. 4,342,840, patented Aug. 3, 1982, Hoffman et al., U.S. Pat. No. 
4,390,645, Jun. 28, 1983, Hoffman, U.S. Pat. No. 4,394,491, Jul. 19, 1983, 
Ramlow et al., U.S. Pat. No. 4,454,255, patented Jun. 12, 1984, Ramlow et 
al., U.S. Pat. No. 4,458,038, Jul. 3, 1984, and Hoffman, U.S. Pat. No. 
4,745,153, patented May 17, 1988. 
As used herein, the following terms shall have the following meanings: 
"monomer"--the simple unpolymerized form of chemical compound having 
relatively low molecular weight, e.g., acrylonitrile, styrene, methyl 
methacrylate, and the like. 
"free radically polymerizable ethylenically unsaturated monomer"--a monomer 
containing ethylenic unsaturation (&gt;C.dbd.C&lt;) that is capable of 
undergoing free radically induced addition polymerization reactions. 
"stability"--the ability of a material to maintain a stable form such as 
the ability to stay in solution or in suspension. 
"polymer polyol"--Such compositions can be produced by polymerizing one or 
more ethylenically unsaturated monomers dissolved or dispersed in a polyol 
in the presence of a free radical catalyst to form a stable dispersion of 
polymer particles in the polyol. These polymer/polyol compositions have 
the valuable property of imparting to, for example, polyurethane foams and 
elastomers produced therefrom, higher load-bearing properties than are 
provided by the corresponding unmodified polyols. 
"viscosity"--in centistokes (cSt) measured at 25.degree. C. on a Cannon 
Fenske viscometer. 
"organic polyisocyanate"--organic compounds that contain at least two 
isocyanato groups and include the hydrocarbon diisocyanates (e.g., the 
alkylene diisocyanates and the arylene diisocyanates), as well as known 
triisocyanates and polymethylene poly(phenylene isocyanates). Illustrative 
polyisocyanates are: 
2,4'-diisocyanatotoluene 
2,6-diisocyanatotoluene 
methylene bis(4-cyclohexyl isocyanate) 
1,2-diisocyanatoethane 
1,3-diisocyanatopropane 
1,2-diisocyanatopropane 
1,4-diisocyanatobutane 
1,5-diisocyanatopentane 
1,6-diisocyanatohexane 
bis(3-isocyanatopropyl)ether 
bis(3-isocyanatopropyl) sulfide 
1,7-diisocyanatoheptane 
1,5-diisocyanato-2,2-dimethylpentane 
1,6-diisocyanato-3-methoxyhexane 
1,8-diisocyanatooctane 
1,5-diisocyanato-2,2,4-trimethypentane 
1,9-diisocyanatononane 
1,10-disocyanatopropyl)ether of 1,4-butylene glycol 
1,11-diisocyanatoundecane 
1,12-diisocyanatododecane bis(isocyanatohexyl) sulfide 
1,4-diisocyanatobenzene 
2,4-diisocyanatotolylene 
2,6-diisocyanatotolylene 
1,3-diisocyanato-o-xylene 
1,3-diisocyanato-m-xylene 
1,3-diisocyanato-p-xylene 
2,4-diisocyanato-1-chlorobenzene 
2,4-diisocyanato-1-nitrobenzene 
2,5-diisocyanato-1-nitrobenzene 
4,4-diphenylmethylene diisocyanate 
3,3-diphenyl-methylene diisocyanate 
polymethylene poly (phenyleneisocyanates) 
and mixtures thereof. 
The preferred polyisocyanates are a mixture of 80% 2,4-tolylene 
diisocyanate and 20% 2,6-tolylene diisocyanate and polymethylene poly 
(phenyleneisocyanates). 
THE INVENTION 
This invention is directed to a novel high potency preformed stabilizer 
composition and to the manufacture of polymer/polyols therewith which 
possesses a combination of 
higher polymer content, greater than 30 weight percent and up to about 60 
weight percent, 
lower viscosities, typically less than about 20,000 cSt, preferably less 
than about 15,000 cSt, most preferably below 10,000 cSt, 
excellent product stability such that 100% passes through a 150 mesh 
screen, 
exceptionally high amounts of the high polymer content polymer/polyol, up 
to 100% thereof, pass through a 700 mesh screen test, 
and improved polyurethanes made therewith. 
This invention is an improvement in the art of polymer/polyols in that it 
recognizes certain unpredictable relationships in composition that 
achieves remarkable reductions in viscosities of polymer/polyols tracking 
a broad range of solids content. The polymer/polyols are notable by being 
essentially free of certain high viscosity byproduct components from the 
manufacture of the polymer phase, that heretofore got dissolved in the 
polyol phase, and undesirably increases its viscosity at the sacrifice of 
the solids content of the polymer/polyol. 
This invention overcomes the disadvantages discovered in prior art 
stabilized polymer/polyols that in their manufacture, stabilizer 
components of high viscosity are not sufficiently incorporated into the 
polymer phase. Because they can be solubilized by the polyol phase, they 
increase its viscosity. This invention further recognizes an important 
relationship in the manner of the stabilizer's formation and its 
composition to the ultimate solids content and viscosity of the 
polymer/polyol. 
This invention relates to: 
a composition for forming high potency preformed stabilizer. 
the novel process for making high potency preformed stabilizer; 
the high potency preformed stabilizer; 
a novel composition for making an enhanced polymer/polyol composition; 
a novel process for making polymer/polyols; 
a novel polymer/polyol composition; and 
unique polyurethanes having high modulus or load-bearing capacity. 
A significant advantage of the invention is the ability to consistently 
make commercially acceptable polymer/polyols having higher polymer 
contents and lower viscosities with smaller amounts of free radical 
catalyst in the formulation. 
This invention achieves a polymer/polyol composition which possesses a 
polymer content of about 30 to about 60 weight percent, based on total 
weight, a viscosity in centistokes less than about 20,000 cSt over the 
range of said polymer content, product stability such that essentially 
100% passes through a 150 mesh screen and significant amounts of the high 
polymer content polymer/polyol, indeed, up to essentially 100% thereof, 
pass through a 700 mesh screen. The composition comprises (I) a liquid 
base polyol having a hydroxyl number of about 10 to about 180 present in 
the composition in an amount of from about 40 to about 70 weight percent 
of the composition, (II) a particulate polymer portion dispersed in the 
liquid base polyol (I) having an average particle size less than about 10 
microns and being stable to settling, comprising free radically 
polymerizable ethylenically unsaturated monomer, such as, (i) 
acrylonitrile and/or (ii) at least one other ethylenically unsaturated 
monomer copolymerizable with acrylonitrile, in the presence of (III) the 
free radical polymerization product of (A) a free radically polymerizable 
ethylenically unsaturated monomer, such as, acrylonitrile and/or at least 
one other ethylenically unsaturated comonomer polymerizable with 
acrylonitrile, and (B) an adduct of a polyhydric alcohol having the 
average formula 
EQU A(OROX).sub.&gt;3 
wherein A is a polyvalent organic moiety, the free valence of which is &gt;3, 
or has an average value of &gt;3, R is the divalent residue comprising an 
alkylene oxide moiety and X is one or more of an organic moiety containing 
reactive unsaturation, copolymerizable with (A), and hydrogen, about one 
of such X is the organic moiety containing reactive unsaturation and the 
remaining X's are hydrogen, (C) optionally adducted with an organic 
polyisocyanate, wherein the amount of (B) or reaction product of (B), 
unreacted with (A), that is contained in the liquid polyol (I) is less 
than about 2 weight percent of the weight of the liquid polyol (I). 
In a preferred embodiment of the invention in polymer/polyol composition, 
(B) is an adduct of a polyhydric alcohol having the average formula 
EQU A(OROX).sub..gtoreq.4 
wherein A is a polyvalent organic moiety, the free valence of which is 
.gtoreq.4, or has an average value of .gtoreq.4, R is the divalent residue 
comprising an alkylene oxide moiety and X is one or more of an organic 
moiety containing reactive unsaturation, copolymerizable with (A), 
preferably a fumaric compound, and hydrogen, about one of such X is the 
organic moiety containing reactive unsaturation and the remaining X's are 
hydrogen. In a further preferred embodiment, the weight ratio of the 
hydroxy-terminated alkylene oxide moieties of (B) comprises 0.2 to 20 
weight percent, on average, of the weight of the particles (II). 
Another aspect of this invention is a high potency preformed stabilizer for 
use in making polymer/polyols comprising the free radical polymerization 
product of (A) a free radically polymerizable ethylenically unsaturated 
monomer and (B) an adduct of a polyhydric alcohol having the average 
formula 
EQU A(OROX).sub.&gt;3 
wherein A is a polyvalent organic moiety, the free valence of which is &gt;3, 
or has an average value of &gt;3, R is the divalent residue comprising an 
alkylene oxide moiety and X is one or more of an organic moiety containing 
reactive unsaturation, copolymerizable with (A), preferably a fumaric 
compound, and hydrogen, about one of such X is the organic moiety 
containing reactive unsaturation and the remaining X's are hydrogen, in 
which the adduct may be further adducted with an organic polyisocyanate. 
A desirable composition, according to this invention, for forming a high 
potency preformed stabilizer [designated as stabilizer (II) herein] for 
use in making polymer/polyols contains: 
(A) a precursor to the stabilizer [designated as precursor (I) herein] 
comprising an esterified product of reaction of: 
(i) a hydroxy-terminated alkylene oxide adduct of a polyol of the formula 
EQU A(OH).sub.&gt;3 
wherein A is a polyvalent organic moiety, the free valence of which is &gt;3, 
or has an average value of &gt;3, and preferably is an organic moiety in 
which the OH bonded thereto comprise about 20 to about 50 weight percent 
of the combined molecular weight of A(OH).sub.&gt;3 ; 
(ii) a mono or polycarbonyloxy compound comprising the moiety 
##STR1## 
(iii) optionally adducted with an organic polyisocyanate; (B) one or more 
ethylenically unsaturated monomers, at least one of which copolymerizes 
with the precursor (I) to the stabilizer; 
(C) a free radical polymerization initiator; and 
(D) a liquid diluent in which (A), (B), and (C) are soluble, but in which 
the resulting high potency preformed stabilizer is essentially insoluble. 
The novel process for making the high potency preformed stabilizer (II) 
comprises providing (A), (B), (C), and (D), above, in a reaction zone 
maintained at a temperature sufficient to initiate a free radical 
reaction, and under sufficient pressure to maintain only liquid phases in 
the reaction zone, for a period of time sufficient to react essentially 
all or all of (A); and recovering a heterogenous mixture containing the 
high potency preformed stabilizer dispersed in the diluent, and unreacted 
monomer to the extent present. 
A novel enhanced polymer/polyol forming composition according to this 
invention, comprises: 
(i) high potency preformed stabilizer (II); 
(ii) a free radically polymerizable ethylenically unsaturated monomer; and 
(iii) a polyol having a hydroxyl number of less than about 180; and 
(iv) a free radical polymerization initiator. 
A novel process for making the enhanced polymer/polyol compositions of the 
invention involves: 
(1) providing a heterogenous mixture of the high potency preformed 
stabilizer (II) and, optionally, liquid diluent (D) above, in combination 
with 
(a) polyol having a hydroxyl number of less than about 180, 
(b) a free radically polymerizable ethylenically unsaturated monomer, 
(c) a free radical polymerization initiator, 
(2) in a reaction zone maintained at a temperature sufficient to initiate a 
free radical reaction, and under sufficient pressure to maintain only 
liquid phases in the reaction zone, for a period of time sufficient to 
react at least a major portion of (b) to form a heterogenous mixture 
containing the enhanced polymer polyol, unreacted monomers and diluent, 
and 
stripping the unreacted monomers and diluent from the enhanced 
polymer/polyol to recover the same. 
A preferred embodiment of the invention includes the use of an acyl 
peroxide of the following formula as the free radical polymerization 
initiator in the polymer/polyol process: 
##STR2## 
wherein R is an organic moiety free of substituents or heteroatoms, 
capable of forming free radical ions in the course of free radical 
polymerization, which adversely affect the physical properties of the 
resultant enhanced polymer/polyol. 
The invention relates to the manufacture of high solids, white 
polymer/polyols possessing lower viscosities without sacrificing 
stability. A feature of the invention includes polymer/polyol compositions 
containing at least 30 weight % polymer, the remainder comprising liquid 
polyol. This product possesses excellent product stability and requires 
less free radical catalyst in its manufacture. 
The invention is ultimately employable in compositions for the manufacture 
of a polymer/polyol polyurethane foams, and the resultant polyurethane 
foam, wherein there is employed a polymer/polyol, a polyurethane catalyst, 
an organic polyisocyanate, a silicone surfactant, and a blowing agent. The 
improvement involves the use as the polymer/polyol in making the 
polyurethane foam, the polymer/polyol composition of this invention, as 
described herein.

DETAILED DESCRIPTION OF INVENTION 
This invention is an improvement on the compositions and processes 
described in U.S. Pat. No. 4,242,249 and European Patent Application 
87114233.7, described above. This invention meets the market needs for 
polymer/polyol compositions containing more than 30 weight percent 
polymer, preferably more than about 40 weight percent polymer, more 
preferably more than about 45 weight percent polymer, most preferably, at 
least about 50, and as high as 60 weight percent polymer, and even higher, 
while at the same time possessing lower viscosities, as correlated to the 
choice of base polyol, than heretofore was believed possible. These 
polymer/polyol compositions possess exceptional performance stability and 
employ lower concentrations of free radical catalyst. The unique 
advantages are most significantly realized with polymer/polyols containing 
more than 45 weight percent polymer, or more than 50 weight percent 
polymer, up to about 60 weight percent polymer. 
Precursors (I) 
Stabilizer precursors (I) are used to make the novel high potency preformed 
stabilizers (II) of the invention. Stabilizers (II), in turn, are used to 
make the polymer/polyols of this invention, functioning to assist in 
imparting a desired stability to the resulting polymer/polyols. Suitable 
precursors (I) are, in general, prepared by the reaction of the selected 
reactive unsaturated compound with an alkoxylated polyol adduct. 
Precursor (I) comprises an adduct of a polyhydric alcohol having the 
average formula 
EQU A(OROX).sub.&gt;3 
wherein A is a polyvalent organic moiety, the free valence of which is &gt;3 
or has an average value of &gt;3, R is the divalent residue comprising an 
alkylene oxide moiety and X is one or more of an organic moiety containing 
reactive unsaturation, copolymerizable with (A), preferably a fumaric 
compound, and hydrogen, about one of such X is the organic moiety 
containing reactive unsaturation and the remaining X's are hydrogen, in 
which the adduct may be further adducted with an organic polyisocyanate,. 
In a preferred embodiment, precursor (I) is an adduct of a polyhydric 
alcohol having the average formula 
EQU A(OROX).sub..gtoreq.4 
wherein A is a polyvalent organic moiety, the free valence of which is 
.gtoreq.4, or has an average value of .gtoreq.4, R is the divalent residue 
comprising an alkylene oxide moiety and X is one or more of an organic 
moiety containing reactive unsaturation, copolymerizable with (A), 
preferably a fumaric compound, and hydrogen, about one of such X is the 
organic moiety containing reactive unsaturation and the remaining X's are 
hydrogen. 
In more preferred embodiments of the invention, the adduct has the average 
formula A(OROX).sub..gtoreq.5, most preferably A(OROX).sub..gtoreq.6, 
where A is a polyvalent organic moiety, the free valence of which is 
.gtoreq.5 or 6, or has an average value of .gtoreq.5 or 6, as the case may 
be, R and X having the meanings set forth above. 
The term "reactive unsaturated compound," that forms X above, means any 
compound having a carbon-to-carbon double bond which is adequately 
reactive with the particular monomer system being utilized. It is 
different from the particular monomer system being used. It is capable of 
adducting with the alkoxylated polyol adduct, either directly or 
indirectly, via one or more of a variety of mechanisms ranging from 
esterification, Michaels Addition, free radical addition, isocyanate 
adducting, Williamson synthesis, and the like. More specifically, 
compounds containing alpha, beta unsaturation are preferred, e.g., those 
conjugated carbonyloxy compounds embraced by the formula: 
##STR3## 
Suitable compounds satisfying this criteria include the maleates, 
fumarates, acrylates, and methacrylates. While not alpha, beta unsaturated 
compounds, polyol adducts formed from substituted vinyl benzenes such as 
chloromethylstyrene may likewise be utilized (adducting with the polyol 
adduct via a Williamson synthesis, and the like), preferably in 
combination with a conjugated carbonyloxy compounds. Illustrative examples 
of suitable alpha, beta unsaturated carbonyloxy compounds which may be 
employed to form the stabilizer precursor include maleic anhydride, 
fumaric acid, dialkyl fumarates, dialkyl maleates, glycol maleates, glycol 
fumarates, isocyanatoethyl methacrylate, methyl methacrylate, hydroxyethyl 
methacrylate, acrylic and methacrylic acid and their anhydride, methacryl 
chloride and glycidyl methacrylate. 
The reactive unsaturated compound may be the reaction product of one or 
more molecules resulting in a structure with the desired qualities of a 
reactive unsaturated compound. For example, hydroxymethyl or hydroxyethyl 
methacrylate can be reacted with a polyol by way of coupling through use 
of an organic polyisocyanate (see U.S. Pat. No. 4,521,546) or by reaction 
with unsaturated monoisocyanate, such as 
1,1-dimethyl-m-isopropenylbenzylisocyanate. 
However, in the practice of this invention, it is preferred that a major 
molar amount, up to 100 percent, of the alpha, beta carbonyloxy 
unsaturated compounds used as the reactive unsaturated compound, have 
fumarate-type unsaturation ("fumarics"), or are unsaturated compounds 
which, under the reaction conditions used in adducting with the 
alkoxylated polyol adduct, form a high proportion of fumarate-type 
unsaturation. Illustrative fumarics are fumaric acid and the fumarates, or 
one or more of maleic acid, maleic anhydride and maleates which are 
isomerized to the fumaric structure on or after adduct formation. 
Preferably, the fumarate structure is provided by the incorporation of 
maleic anhydride and the isomerization of the ester to fumarate by known 
treatment with morpholine. 
The alkoxylated polyol adduct is desirably a hydroxy-terminated alkylene 
oxide adduct of "starter" higher hydroxylated alcohols of the formula: 
EQU A(OH).sub.&gt;3 
and preferably a "starter" tetraol and higher hydroxylated alcohols, of the 
formula: 
EQU A(OH).sub..gtoreq.4 
wherein A is a polyvalent organic moiety, the free valence of which is &gt;3 
or .gtoreq.4, or an average value equal thereto, as the case may be. 
Illustrative of suitable compounds embraced by the "starter" 
A(OH).sub..gtoreq.4 alcohol are the following: pentaerythritol, sorbitol, 
diether of sorbitol, mannitol, diether of mannitol, arabitol, diether of 
arabitol, sucrose, oligomer of polyvinyl alcohol or glycidol, connected 
branched chain polyols, mixtures thereof, and the like. 
In more preferred embodiments of the invention, the starter alcohol has the 
average formula A(OH).sub..gtoreq.5, most preferably A(OH).sub..gtoreq.6, 
where A is a polyvalent organic moiety, the free valence of which is 
.gtoreq.5 or 6, or has an average value of .gtoreq.5 or 6, as the case may 
be. 
The starter A(OH).sub.&gt;3 or .gtoreq.4 or .gtoreq.5 or .gtoreq.6 is first 
reacted with 1,2-alkylene oxide in an amount and under conditions 
sufficient to convert its hydroxyl groups to hydroxyalkyl groups. The 
amount of 1,2-alkylene oxide reacted is sufficient to achieve the ultimate 
molecular weight of the alkoxylated polyol adduct that is to be reacted 
with the fumaric component to form precursor (I). The molecular weight of 
the alkoxylated polyol adduct should be relatively high, preferably above 
about 4000 (number average) and, more preferably, above about 5000. The 
minimum molecular weight of the alkoxylated polyol adduct may be about 
3000. The preferred 1,2-alkylene oxides are lower 1,2-alkylene oxides, 
such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, and the 
like. In the preferred practice of the invention, the starter 
A(OH).sub..gtoreq.4 is reacted with 1,2-propylene oxide in an amount 
sufficiently to create the desired polyol molecular weight. Then, the 
resulting polyol may be hydroxyethyl capped by reaction with 1,2-ethylene 
oxide to provide assurance of primary hydroxyl content in the polyol 
especially if the alkoxylated polyol adduct is subsequently coupled, not 
polymerized, with an organic polyisocyanate. Such alkoxylation reactions, 
with consequent adduct formation, is well known in the art, and forms no 
part of this invention. Adduct reactions may be base or acid catalyzed, 
with base catalyzation preferred. 
The alkoxylated polyol adduct is then reacted with a reactive unsaturated 
compound to introduce the desired degree of unsaturation. In the preferred 
practice of the invention, the reactive unsaturation is introduced through 
esterification with the hydroxyl groups of the alkoxylated polyol adduct 
by reaction with an alpha, beta carbonyloxy unsaturated compound in which 
the carbonyloxy is part of a carboxylic acid, anhydride or ester group. 
For example, one mole of a polyol may be reacted with one mole of maleic 
anhydride to form a half ester of maleic acid. The free carboxylic acid 
group is typically not further reacted with polyol, but rather, is reacted 
with 1,2-alkylene oxide such as 1,2-ethylene oxide so as to cap the free 
carboxyl groups in the esterified product. Thereafter, as an optional 
feature, the alkoxylated polyol adduct ester may be coupled, not 
polymerized, with organic polyisocyanate. Such combination of reactions 
produce the stabilizer precursor (I). 
The amount of ethylenic unsaturation in the stabilizer precursor (I) may 
vary to a significant extent. The minimum and maximum levels of 
unsaturation are dictated by the dispersion stability that the precursor 
(I) imparts through the subsequently formed preformed stabilizer (II), and 
hence to the polymer/polyol composition. 
The minimum amount of unsaturation is that amount which impacts on the 
dispersion stability of the polymer/polyol. Typically, the lower limit of 
unsaturation is about 0.5 moles of the reactive unsaturated compound per 
mole of the alkoxylated polyol adduct ester. The maximum amount of 
unsaturation is that amount which causes an undesirable amount of 
cross-linking of the stabilizer precursor (I). When higher amounts of 
unsaturation are present during preparation of the stabilizer precursor 
(I), there is a greater probability that species will be formed having 
more than one double bond per molecule. An undue population of 
cross-linking could adversely affect the stabilizer's (II) ability to 
provide dispersion stability enhancement and, as well, cause it to have a 
significantly increased viscosity. Accordingly, the maximum amount of 
unsaturation provided should be below that at which significant 
cross-linking occurs. 
The desired amount of reactive unsaturated compound to be used in making 
precursor (I) will depend on the molecular weight of the alkoxylated 
polyol adduct. Typically, it will be desirable to employ about 0.5 to 
about 1.5 moles of the reactive unsaturated compound for each mole of the 
alkoxylated polyol adduct. Preferably, about 0.7 to about 1.1 moles of the 
reactive unsaturated compound for each mole of the alkoxylated polyol 
adduct, are employed to make precursor (I). Less of the reactive 
unsaturated compound may be used, but if lesser amounts are used, one 
should contemplate the need for using larger amounts of the thus made 
precursor (I) in making stabilizer (II). It is preferred to prepare the 
precursor (I) in such a fashion that the unsaturation is retained to the 
maximum extent possible. 
Loss of unsaturation may occur in stabilizer precursor (I) preparation with 
any of the alpha, beta unsaturated compounds. For example, it has been 
recognized that when maleic anhydride is employed anywhere from about 25 
percent to essentially all of the unsaturation may be lost. Loss in 
unsaturation appears to be generally accompanied by an increase in 
viscosity of precursor (I). Accordingly, it is desirable to utilize an 
efficient process in the preparation of the precursor such that at least 
one-quarter (1/4) of the added unsaturation is retained. 
Precursor (I) preparation is preferably carried out in the presence of a 
catalytic amount of a strong base. Suitable bases include inorganic bases 
such as alkali and alkaline earth metal hydroxides and the weak acid salts 
of alkali and alkaline earth metals, and organic bases such as quaternary 
ammonium hydroxides, 4-dimethylaminopyridine, 4-pyrrolidinopyridine, and 
imidazole. Potassium hydroxide has been found to be useful. The amount of 
catalyst is not critical; and may, for example, be as low as about 10 ppm. 
or even less when potassium hydroxide is used. 
For example, in esterifying the alkoxylated polyol adduct to introduce the 
fumarate structure, stabilizer precursor (I) having an adequate viscosity 
may be obtained using about 20 parts per million of potassium hydroxide. 
This typically allows retention of about 50 percent of the unsaturation, 
with up to about 70 percent of the unsaturation being of the fumarate 
type, under reasonably appropriate reaction times and conditions. 
Viscosities of about 3000 cSt are typically provided. 
Suitable reaction temperatures may vary from about 100 to about 125.degree. 
C. up to about 180.degree. C., or higher. Desirably, the reaction should 
be carried out in a reactor capable of agitation and subsequent 
pressurization. Alkylene oxide, preferably ethylene or propylene oxide, 
either with the other reactants or subsequently, may be added to the 
reactor to the extent it may be necessary to reduce the acid number of the 
alkoxylated polyol adduct. The acid number of the alkoxylated polyol 
adduct should preferably be below about 3.0, most preferably below about 
1.0, but not so low as to cause a viscosity increase with accompanying 
loss of unsaturation. The product may then be cooled and stripped to 
remove excess alkylene oxide. It is then ready for use in preparing the 
preformed stabilizer (II). If the fumaric structure is provided by the use 
of maleic anhydride or acid or ester, then the esterification product is 
treated with morpholine to convert the maleate units in the precursor 
structure to fumarate units in the desired concentration. 
In the usual case, the maximum viscosity of useful precursor (I) will be 
dictated by practical considerations, such as: the viscosity of precursor 
(I) should not be so high that it cannot be conveniently handled. 
Viscosities up to about 10,000 cSt to about 15,000 cSt may be 
satisfactorily handled but it is preferred that the viscosity be less than 
about 8,000 cSt. 
Accordingly, precursor (I) may be made by reacting a sorbitol-initiated 
polyol with maleic anhydride in the presence of potassium hydroxide 
catalyst. This may be accomplished by using a temperature of about 
125.degree. C. to preserve a high proportion of the charged (i.e. added) 
unsaturation. The maleate unsaturation may then be isomerized to fumarate 
using morpholine at some lower temperature, such as 80.degree. C. 
Alternatively, higher temperatures (e.g. about 175.degree. to about 
180.degree. C. or so) may be utilized to achieve relatively high levels of 
fumarate-type unsaturation directly. The techniques involved are well 
known and may be used as desired. 
Viscosity adjustment can be effected by reacting the fumarate ester product 
with an organic isocyanate such as an organic polyisocyanate at moderate 
temperatures, e.g., about 60.degree. to about 80.degree. C. In such cases, 
the amount of reaction is intended to achieve a relative minor amount of 
viscosity increase, therefore small amounts of the isocyanate are 
employed. 
High Potency Preformed Stabilizers (II) 
The high potency preformed stabilizer for use in making polymer/polyols 
comprising the free radical polymerization product of (A) a free radically 
polymerizable ethylenically unsaturated monomer and (B) an adduct of a 
polyhydric alcohol having the average formula 
EQU A(OROX).sub.&gt;3 
wherein A is a polyvalent organic moiety, the free valence of which is &gt;3, 
or has an average value equal thereto, R is the divalent residue 
comprising an alkylene oxide moiety and X is one or more of an organic 
moiety containing reactive unsaturation, copolymerizable with (A), 
preferably a fumaric compound, and hydrogen, about one of such X is the 
organic moiety containing reactive unsaturation and the remaining X's are 
hydrogen, in which the adduct may be further adducted with an organic 
polyisocyanate. 
The high potency preformed stabilizer (II) of the invention is derived from 
the following composition, comprising: 
(A) precursor (I); 
(B) a free radically polymerizable ethylenically unsaturated monomer, 
preferably acrylonitrile and at least one other ethylenically unsaturated 
comonomer copolymerizable therewith, 
(C) a free radical polymerization initiator; and 
(D) a liquid diluent in which (A), (B), and (C) are soluble, but in which 
the resulting high potency preformed stabilizer (II) is essentially 
insoluble. 
In another embodiment, the invention relates to a novel process for making 
the high potency preformed stabilizer (II) which comprises providing (A), 
(B), (C), and (D), above, in a reaction zone maintained at a temperature 
sufficient to initiate a free radical reaction, and under sufficient 
pressure to maintain only liquid phases in the reaction zone, for a period 
of time sufficient to react essentially all or all of (A); and recovering 
a heterogenous mixture containing the high potency preformed stabilizer 
(II) dispersed in the diluent. 
Item (B) above, may be the aforementioned reactive unsaturated compounds, 
particularly those that are free radically polymerizable. Preferably, (B) 
is acrylonitrile and at least one other ethylenically unsaturated 
comonomer copolymerizable with acrylonitrile. Illustrations of 
ethylenically unsaturated comonomer copolymerizable with acrylonitrile 
include styrene and its derivatives, acrylates, methacrylates such as 
methyl methacrylate, vinylidene chloride, and the like. 
It is preferred to utilize acrylonitrile with a comonomer and to maintain a 
minimum of about 5 to 15 percent by weight acrylonitrile in the system. 
Styrene will generally be preferred as the comonomer, but methyl 
methacrylate or other monomers may be employed in place of part or all of 
the styrene. The preferred monomer mixture (B) used to make the stabilizer 
(II) composition comprises mixtures of acrylonitrile and styrene. The 
weight proportion of acrylonitrile can range from about 20 to 80 weight 
percent of the comonomer mixture, more typically from about 30 to about 40 
weight percent, and styrene can accordingly vary from about 80 to about 20 
weight percent of the mixture. An acrylonitrile to styrene ratio in the 
monomer mixture of from about 25:75 to 45:55 is particularly preferred, 
even more particularly about 30:70 to 40:60. 
The free radical polymerization initiator useful with respect to item (C) 
encompasses any free radical catalyst suitable for grafting of an 
ethylenically unsaturated polymer to a polyol. Useful catalysts include 
catalysts having a satisfactory half-life within the temperature ranges 
used in forming the stabilizer (II), i.e.-the half-life should be about 25 
percent or less of the residence time in the reactor at a given 
temperature. Representative examples of useful catalyst species include 
t-butyl peroxy-2-ethylhexanoate, t-butylperpivalate, t-amyl peroctoate, 
2,5-dimethyl-hexane-2,5-di-per-2-ethyl hexoate, t-butylperneodecanoate, 
and t-butylperbenzoate. Useful also are the azo catalysts such as 
azobis-isobutyronitrile, 2,2'-azo bis-(2-methylbutyronitrile), and 
mixtures thereof. The preferred free radical catalysts are peroxides such 
as tertiary butyl peroctoate. 
The catalyst concentration in the formulation is not critical and can be 
varied within wide limits. As a representative range, the concentration 
can vary from about 0.01 to about 2.0 weight percent or even more, 
preferably about 0.05 to about 0.10 weight percent, based upon the total 
feed to the reactor. Up to a certain point, increases in the catalyst 
concentration result in increased monomer conversion and grafting; but 
further increases do not substantially increase conversion. Catalyst 
concentrations which are too high can cause cross-linking in the preformed 
stabilizer (II). The particular catalyst concentration selected will 
usually be an optimum value considering all factors, including costs. 
The liquid diluent (D) in which (A), (B), and (C) are soluble, but in which 
the resulting high potency preformed stabilizer (II) is essentially 
insoluble, comprises either a single diluent or a mixture of diluents. 
Such diluents can be mono-ols (monohydroxy alcohols), polyols, 
hydrocarbons, ethers, and the like liquids. As long as the diluent does 
not adversely affect the performance of the preformed stabilizer (II), it 
is suitable for use in the practice of the invention. Preferred are the 
mono-ols because of their ease of stripping from the final polymer/polyol 
composition. Mixtures of mono-ol and polyol may be used as diluents. In 
that case, the polyol need not be stripped off. The choice of mono-ol is 
not narrowly critical. It should not form two phases at reaction 
conditions and should be readily stripped from the final polymer/polyol. 
The selection of mono-ol is typically an alcohol containing at least one 
carbon atoms, such as methanol, ethanol, n-propanol, i-propanol, 
n-butanol, sec.-butanol, t-butanol, n-pentanol, 2-pentanol, 3-pentanol, 
and the like, and mixtures of the same. The preferred mono-ol is 
isopropanol. The concentration of polyol in the diluent composition (D) if 
used, is limited to an amount below which gelling occurs in preformed 
stabilizer (II). 
The polyol component of diluent (D) is typically the alkylene oxide adduct 
of A(OH).sub..gtoreq.4 describe above. Though the polyol used in diluent 
(D) can encompass the variety of polyols described above, including the 
broader class of polyols described in U.S. Pat. No. 4,242,249, patented 
Dec. 30, 1980, at column 7, line 39 through column 9, line 10, which 
disclosure is incorporated herein by reference, it is preferred that the 
polyol component of diluent (D) be the same as or equivalent to the polyol 
used in the formation of precursor (I). 
If a mixture of a mono-ol and a polyol is used as diluent (D) it is 
desirable that the polyol comprise the minor amount by weight of diluent 
(D) and the mono-ol the major amount. In the usual case, the polyol will 
comprise less than about 30 weight percent of the weight of diluent (D). 
Preferably, the polyol comprises less than about 20 weight percent of 
diluent (D), most preferably less than about 15 weight percent. In any 
case, the polyol portion will be below that concentration at which gelling 
occurs in preparing the preformed stabilizer (II). 
Because of the number of components, the variability of their concentration 
in the feed, and the variability of the operating conditions of 
temperature, pressure, and residence or reaction times, a substantial 
choice of them are possible and still achieve the benefits of the 
invention. Therefore, it is prudent to test particular combinations to 
confirm the most suitable operating mode for producing a particular final 
polymer/polyol product. 
In general, the amount of the components in the formulation, on a weight 
percent of the total formulation for forming stabilizer (II), is as 
follows: 
______________________________________ 
Component of 
Formulation Amount, weight % 
______________________________________ 
A about 10 to 40 
B about 10 to 30 
C about 0.01 to 2 
D about 30 to 80 
______________________________________ 
The process for producing the high potency preformed stabilizer (II) is 
similar to the process for making the polymer/polyol. The temperature 
range is not critical and may vary from about 80.degree. C. to about 
150.degree. C. or perhaps greater, the preferred range being from 
115.degree. C. to 125.degree. C. The catalyst and temperature should be 
selected so that the catalyst has a reasonable rate of decomposition with 
respect to the hold-up time in the reactor for a continuous flow reactor 
or the feed time for a semi-batch reactor. 
The mixing conditions employed are those obtained using a back mixed 
reactor (e.g. -a stirred flask or stirred autoclave). The reactors of this 
type keep the reaction mixture relatively homogeneous and so prevent 
localized high monomer to precursor (I) ratios such as occur in tubular 
reactors, where all of the monomer is added at the beginning of the 
reactor. 
The preformed stabilizer (II) of the present invention comprise dispersions 
in the diluent and any unreacted monomer in which the preformed stabilizer 
(II) is probably present as individual molecules or as groups of molecules 
in "micelles," or on the surface of small polymer particles. 
The combination of conditions selected should not lead to cross-linking or 
gel formation in the preformed stabilizer (II) which can adversely affect 
the ultimate performance in making the polymer/polyol composition. 
Combinations of too low a diluent concentration, too high a precursor (I) 
and/or monomer concentration, too high a catalyst concentration, too long 
of a reaction time, and too much unsaturation in precursor (I) can result 
in ineffective preformed stabilizer (II) from cross-linking or gelling. 
Novel Polymer/Polyols (III) 
As pointed out above, the invention relates to the manufacture of high 
solids, white polymer/polyols possessing lower viscosities without 
sacrificing stability. The invention relates to polymer/polyol 
compositions containing at least 30 weight % polymer, the remainder 
comprising liquid polyol. This product possesses excellent product 
stability and uses less free radical catalyst in its manufacture. 
This invention achieves a polymer/polyol composition which possesses a 
polymer content of about 30, preferably about 40, more preferably about 
45, and most preferably about 50, to about 60 weight percent. Over the 
range of solids content, it can have a viscosity in centistokes less than 
about 20,000 cSt, such that the lower solids containing polymer/polyols 
can have a viscosity in the range of about 2,000 to about 5,000 (solids of 
about 30-45 weight %). Significantly, these polymer/polyols exhibit 
unique product stability such that essentially 100% passes through a 150 
mesh screen and significant amounts of the high polymer content 
polymer/polyol, up to essentially 100% thereof, pass through a 700 mesh 
screen. As shown in the examples, polymer/polyols having a solids content 
of 50%, with a viscosity of about 5,900, passed essentially 100% through a 
700 mesh screen, and a polymer/polyols having a solids content of 55.3%, 
with a viscosity of about 10,107, passed essentially 40% through a 700 
mesh screen. A truly remarkable illustration of the invention is shown in 
example 8 where a polymer/polyol containing 59.9 weight % polymer had a 
viscosity of 13,176 and 19% passed through a 700 mesh screen. In table IV, 
infra, example 199 taken from U.S. Pat. No. 4,242,249, by comparison, 
dramatizes the advantages of the invention. 
The composition comprises (I) a liquid base polyol having a hydroxyl number 
of about 10 to about 180 present in the composition in an amount of from 
about 40 to about 70 weight percent of the composition, (II) a particulate 
polymer portion dispersed in the liquid base polyol (I) having an average 
particle size less than about 10 microns and being stable to settling, 
comprising a free radically polymerizable ethylenically unsaturated 
monomer, such as, (i) free radical polymerized acrylonitrile and (ii) at 
least one other ethylenically unsaturated comonomer copolymerizable with 
acrylonitrile, in the presence of (III) the free radical polymerization 
product of (A) a free radically polymerizable ethylenically unsaturated 
monomer, such as, acrylonitrile and at least one other ethylenically 
unsaturated comonomer copolymerizable with acrylonitrile, and (B) an 
adduct of a polyhydric alcohol having the average formula 
EQU A(OROX).sub.&gt;3 
wherein A is a polyvalent organic moiety, the free valence of which is &gt;3, 
or has an average value of &gt;3, R is the divalent residue comprising an 
alkylene oxide moiety and X is one or more of an organic moiety containing 
reactive unsaturation copolymerizable with (A), and hydrogen, about one of 
such X is the organic moiety containing reactive unsaturation and the 
remaining X's are hydrogen, (C) optionally adducted with an organic 
polyisocyanate, wherein the amount of (B) or reaction product of (B), 
unreacted with (A), that is contained in the liquid polyol (I) is less 
than about 2 weight percent of the weight of the liquid polyol (I). 
In a preferred embodiment of the invention in polymer/polyol composition, 
(B) is an adduct of a polyhydric alcohol having the average formula 
EQU A(OROX).sub..gtoreq.4 
wherein A is a polyvalent organic moiety, the free valence of which is 
.gtoreq.4, or has an average value of .gtoreq.4, R is the divalent residue 
comprising an alkylene oxide moiety and X is one or more of an organic 
moiety containing reactive unsaturation copolymerizable with (A), 
preferably a fumaric compound, and hydrogen, about one of such X is the 
organic moiety containing reactive unsaturation and the remaining X's are 
hydrogen. In a further preferred embodiment, the weight ratio of the 
hydroxy-terminated alkylene oxide moeities of (B) comprises 0.2 to 20 
weight percent, on average, of the weight of the particles (II). 
The novel enhanced polymer/polyol (III) forming composition of this 
invention comprises: 
(i) the high potency preformed stabilizer (II); 
(ii) a free radically polymerizable ethylenically unsaturated monomer, such 
as, acrylonitrile and at least one other ethylenically unsaturated 
comonomer copolymerizable therewith; 
(iii) a polyol having a hydroxyl number of less than about 180; 
(iv) a free radical polymerization initiator; and 
(v) optionally, diluent (D) characterized above. 
The process for making these novel enhanced polymer/polyol (III) 
compositions comprises: 
(1) providing a heterogenous mixture of the high potency preformed 
stabilizer (II) and, optionally, the diluent (D) in combination with 
(a) a polyol having a hydroxyl number of less than about 180, 
(b) a free radically polymerizable ethylenically unsaturated monomer, such 
as, acrylonitrile and at least one other ethylenically unsaturated 
comonomer copolymerizable therewith, and 
(c) a free radical polymerization initiator, 
in a reaction zone maintained at a temperature sufficient to initiate a 
free radical reaction, and under sufficient pressure to maintain only 
liquid phases in the reaction zone, for a period of time sufficient to 
react a high proportion of (b) to form a dispersion containing the 
enhanced polymer polyol (III) and unreacted monomers and diluent, and 
stripping the unreacted monomers and diluent from the enhanced 
polymer/polyol (III) to recover the same. 
The process of the invention is notable for, over time, not being subject 
to fluctuations in polymer particle average size and polymer/polyol 
product viscosity. This is an advantage over processes which directly feed 
the precursor (I) to reaction with the polyol in directly forming the 
polymer/polyol. 
In a preferred process, the free radical polymerization initiator is an azo 
compound or an acyl peroxide of the formula: 
##STR4## 
wherein R is an organic moiety free of substituents or heteroatoms capable 
of forming free radical ions in the course of free radical polymerization 
which adversely affect the physical properties of the resultant enhanced 
polymer/polyol. Of the azo initiators, azo-bis(isobutyronitrile), 2,2'-azo 
bis-(2-methylbutyronitrile), and mixtures thereof, are preferred. 
Preferred acyl peroxides are the diacyl peroxides in which the acyl 
moieties are alkanoyl containing about 8 to about 14 carbon atoms, 
preferably from about 9 to about 13 carbon atoms. Particularly preferred 
diacyl peroxides are didecanoyl peroxide and dilauroyl peroxide. 
The polyols having a hydroxyl number of less than about 180 comprises 
poly(oxypropylene) blycols, triols and higher functionality polyols. Such 
polyols include poly(oxypropylene-oxyethylene) polyols: however, 
desirably, the oxyethylene content should comprise less than about 50 
percent of the total and, preferably, less than about 20 percent. The 
ethylene oxide can be incorporated in any fashion along the polymer chain. 
Stated another way, the ethylene oxide can be either incorporated in 
internal blocks, as terminal blocks, or may be randomly distributed along 
the polymer chain. As is well known in the art, the preferred polyols 
herein do contain varying amounts of unsaturation. The extent of 
unsaturation typically involved does not affect in any adverse way the 
formation of the polymer/polyols in accordance with the present invention. 
For the purposes of this invention, useful polyols should have a number 
average molecular weight of about 600 or greater, the number average being 
used herein being the theoretical, hydroxyl number derived value. The true 
number average molecular weight may be somewhat less, depending upon the 
extent to which the true molecular functionality is below the starting or 
theoretical functionality. 
The polyols employed can have hydroxyl numbers which vary over a wide 
range. In general, the hydroxyl numbers of the polyols employed in the 
invention can range from about 10 and lower, to about 180, preferably, to 
about 150, more preferably, to about 100, most preferably, to about 75. 
The hydroxyl number is defined as the number of milligrams of potassium 
hydroxide required for the complete hydrolysis of the fully phthalylated 
derivative prepared from 1 gram of polyol. The hydroxyl number can also be 
defined by the equation: 
EQU OH=(56.1.times.1000.times.f)/m.w. 
where 
OH=hydroxyl number of the polyol 
f=functionality, i.e., average number of hydroxyl groups per molecule of 
polyol 
m.w.=molecular weight of the polyol. 
The exact polyol employed depends upon the end use of the polyurethane 
product to be produced. The molecular weight or the hydroxyl number is 
selected properly to result in flexible or semi-flexible foams or 
elastomers when the polymer/polyol produced from the polyol is converted 
to a polyurethane. The polyols preferably possess a hydroxyl number of 
from about 50 to about 150 for semi-flexible foams and from about 10 to 
about 70 for flexible foams. Such limits are not intended to be 
restrictive, but are merely illustrative of the large number of possible 
combinations of the above polyol coreactants. 
While not preferred, any other type of known polyol may also be used. Among 
the polyols which can be employed are one or more polyols from the 
following classes of compositions, known to those skilled in the 
polyurethane art: 
(a) Alkylene oxide adducts of non-reducing sugars and sugar derivatives; 
(b) Alkylene oxide adducts of phosphorus and polyphosphorus acids; 
(c) Alkylene oxide adducts of polyphenols; 
(d) The polyols from natural oils such as castor oil, and the like; 
(e) Alkylene oxide adducts of polyhydroxyalkanes other than those already 
described herein. 
Illustrative alkylene oxide adducts of polyhydroxyalkanes include, among 
others, the alkylene oxide adducts of 1,3-dihydroxypropane, 
1,3-dihydroxybutane, 1,4-dihydroxybutane, 1,4-, 1,5- and 
1,6-dihydroxyhexane, 1,2-, 1,3-, 1,4-, 1,6-, and 1,8-dihydroxyoctane, 
1,10-dihydroxydecane, glycerol, 1,2,4-trihydroxybutane, 
1,2,6-trihydroxyhexane, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, 
pentaerythritol, caprolactone, polycaprolactone, xylitol, arabitol, 
sorbitol, mannitol, and the like. 
A further class of polyols which can be employed are the 1,2-alkylene oxide 
adducts of the non-reducing sugars, wherein the alkylene oxides have from 
2 to 4 carbon atoms. Among the non-reducing sugars and sugar derivatives 
contemplated are sucrose, alkyl glycosides such as methyl glucoside, ethyl 
glucoside, and the like, glycol glycosides such as ethylene glycol 
glucoside, propylene glycol glucoside, glycerol glucoside, 
1,2,6-hexanetriol glucoside, and the like, as well as the alkylene oxide 
adducts of the alkyl glycosides as set forth in U.S. Pat. No. 3,073,788. 
A still further useful class of polyol is the polyphenols, and preferably 
the alkylene oxide adducts thereof wherein the alkylene oxides have from 2 
to 4 carbon atoms. Among the polyphenols which are contemplated are, for 
example, bisphenol A, bisphenol F, condensation products of phenol and 
formaldehyde, the novalac resins; condensation products of various 
phenolic compounds and acrolein; the simplest members of this class being 
the 1,1,3-tris(hydroxyphenyl) propanes, condensation products of various 
phenolic compounds and glyoxal, glutaraldehyde, and other dialdehydes, the 
simplest members of this class being the 1,1,2,2-tetrakis 
(hydroxyphenol)ethanes, and the like. 
The alkylene oxide adducts of phosphorus and polyphosphorus acids are 
another useful class of polyols. Ethylene oxide, 1,2-epoxypropane, the 
epoxybutanes, 3-chloro-1,2-epoxypropane, and the like are preferred 
alkylene oxides. Phosphoric acid, phosphorus acid, the polyphosphoric 
acids such as tripolyphosphoric acid, the polymetaphosphoric acids, and 
the like are desirable for use in this connection. 
It should be appreciated that blends or mixtures of various useful polyols 
may be used if desired. With polyols other than the preferred type, useful 
monomer contents and monomer or monomers may vary somewhat. Similarly, it 
may be desirable or even necessary to modify the stabilizer of this 
invention when such other polyols are used. This can be accomplished by 
following the criteria discussed hereinafter in connection with the 
stabilizers used for the preferred polyols. 
The monomer for making the polymer component may be an ethylenically 
unsaturated monomer, preferably acrylonitrile alone or acrylonitrile and 
at least one other ethylenically unsaturated comonomer copolymerizable 
with acrylonitrile. Illustrative comonomers are styrene and its 
derivatives, acrylates, methacrylates such as methyl methacrylate, 
vinylidene chloride, and the like. 
It is preferred to utilize acrylonitrile mixtures with a comonomer, 
typically with a minimum of about 5 to 15 percent by weight acrylonitrile 
in the system. Styrene will generally be preferred as the comonomer, but 
methyl methacrylate, vinylidene chloride, or other monomers may be 
employed in place of part or all of the styrene. Overall, in terms of the 
final polymer/polyol composition, to provide polymer/polyols for use in 
applications where minimal scorch is desired, the acrylonitrile content of 
the monomer mixture used should be less than about 40 percent by weight, 
preferably less than about 35 percent. 
The free radical polymerization initiator useful in making the 
polymer/polyol encompasses any free radical catalyst suitable for 
polymerizing the monomers to the polymer. Useful catalysts include 
catalysts having a satisfactory half-life within the temperature ranges 
used in forming the stabilizer (II), i.e.-the half-life should be about 25 
percent or less of the residence time in the reactor at a given 
temperature. Representative examples of useful catalyst species include 
acyl peroxides such as didecanoyl peroxide and dilauroyl peroxide, alkyl 
peroxides such as t-butyl peroxy-2-ethylhexanoate, t-butylperpivalate, 
t-amyl peroctoate, 2,5-dimethyl-hexane-2,5-di-per-2-ethyl hexoate, 
t-butylperneodecanoate, t-butylperbenzoate and 1,1-dimethyl-3-hydroxybutyl 
peroxy-2-ethylhexanoate, and azo catalysts such as 
azobis(isobutyronitrile), 2,2'-azo bis-(2-methylbutyronitrile), and 
mixtures thereof. Most preferred are the acyl peroxides of the above 
formula and the azo catalysts. 
The catalyst concentration employed is not critical and can be varied 
considerably. As a representative range, the concentration can vary from 
about 0.1 to about 5.0 weight percent or even more, based upon the total 
feed to the reactor. Up to a certain point, increases in the catalyst 
concentration result in increased monomer conversion; but further 
increases do not substantially increase conversion. The particular 
catalyst concentration selected will usually be an optimum value 
considering all factors, including costs. It has been determined that 
lower concentrations can be used in conjunction with the high potency 
preformed stabilizer (II) and still achieve stable polymer/polyols. 
Particularly preferred in the practice of the invention, are the use of azo 
catalysts and the aforementioned acyl peroxides of the above formula. Such 
acyl peroxides have the unique advantage of effecting the desired degree 
of polymerization essentially without raising the viscosity of the 
polymer/polyol over that obtained with the azo catalyst. This enhances 
one's ability to achieve higher solids polymer/polyols with good product 
stability without raising product viscosity. Such acyl peroxides can be 
used in molar amounts substantially less than the amounts required when 
using other free radical catalysts in forming the polymer/polyols. 
The polymer/polyols are preferably produced by utilizing a low monomer to 
polyol ratio is maintained throughout the reaction mixture during the 
process. This is achieved by employing conditions that provide rapid 
conversion of monomer to polymer. In practice, a low monomer to polyol 
ratio is maintained, in the case of semi-batch and continuous operation, 
by control of the temperature and mixing conditions and, in the case of 
semibatch operation, also by slowly adding the monomers to the polyol. 
The temperature range is not critical and may vary from about 100.degree. 
C. to about 140.degree. C. or perhaps greater, the preferred range being 
from 115.degree. C. to 125.degree. C. As has been noted herein, the 
catalyst and temperature should be selected so that the catalyst has a 
reasonable rate of decomposition with respect to the hold-up time in the 
reactor for a continuous flow reactor or the feed time for a semi-batch 
reactor. 
The mixing conditions employed are those obtained using a back mixed 
reactor (e.g.-a stirred flask or stirred autoclave). The reactors of this 
type keep the reaction mixture relatively homogeneous and so prevent 
localized high monomer to polyol ratios such as occur in tubular reactors 
when such reactors are operated with all the monomer added to the 
beginning of the reactor. 
The polymer/polyols of the present invention comprise dispersions in which 
the polymer particles (the same being either individual particles or 
agglomerates of individual particles) are relatively small in size and, in 
the preferred embodiment, have a weight average size less than about ten 
microns. However, when high contents of styrene are used, the particles 
will tend to be larger; but the resulting polymer/polyols are highly 
useful, particularly where the end use application requires as little 
scorch as possible. 
In the preferred embodiment, all of the product (viz. 100%) will pass 
through the filter employed in the 150 mesh filtration hinderance 
(filterability) test that will be described in conjunction with the 
Examples. This insures that the polymer/polyol products can be 
successfully processed in all types of the relatively sophisticated 
machine systems now in use for large volume production of polyurethane 
products, including those employing impingement-type mixing which 
necessitate the use of filters that cannot tolerate any significant amount 
of relatively large particles. In addition, a significant amount of the 
polymer/polyol passes the 700 mesh filtration hindrance test, as 
characterized more fully in the examples. It should be appreciated that 
the 700 mesh filtration hindrance test presents the most rigorous test of 
polymer/polyol stability. 
______________________________________ 
As used in the Examples, the following designations, symbols, 
terms and abbreviations have the following meanings: 
______________________________________ 
Polyol A A polyol made by reacting propylene oxide and 
ethylene oxide with sorbitol in the presence 
of potassium hydroxide catalyst and refining to 
remove catalyst. The polyol contains about 8 
weight percent ethylene oxide as a cap and 
has a hydroxyl number of about 28. 
Polyol B A polyol made by reacting propylene oxide and 
ethylene oxide with sorbitol in the presence 
of potassium hydroxide catalyst and refining 
to remove catalyst. The polyol contains 
about 8 weight percent ethylene oxide as an 
internal block and has a hydroxyl number 
of about 28. 
Polyol C A polyol made by reacting propylene oxide and 
ethylene oxide with glycerol in the presence of 
potassium hydroxide catalyst and refining to 
remove catalyst. The polyol contains about 
10 weight percent internal ethylene oxide 
and has a hydroxyl number of about 52. 
Polyol D A polyol made by reacting propylene oxide 
and ethylene oxide successively with 
glycerol in the presence of potassium 
hydroxide catalyst and refining to remove 
catalyst. The polyol contains about 19 
weight percent ethylene oxide as a cap 
and has hydroxyl number of about 35. 
Azo catalyst 
Azo-bis(isobutyronitrile) 
Catalyst A 
A polyurethane foam amine catalyst sold as 
"NIAX Catalyst A-1" by Union Carbide 
Corporation. 
Catalyst B 
A polyurethane tin catalyst sold as "T-9". 
Surfactant A 
A silicone surfactant sold for use in foam by 
Union Carbide Corporation as "Silicone 
Surfactant L-6202". 
Isocyanate A 
Modified liquid form of 4,4'-diphenylmethane 
diisocyanate (MDI) having an equivalent weight of 
143 sold as "Isonate 143L" by the Dow 
Chemical Company. 
TDI A mixture of 80 weight percent 2,4- 
diisocyanatotoluene and 20 weight percent 2,6- 
diisocyanatotoluene. 
Density Density in pounds per cubic foot (ASTM D-3574, 
Test A). 
Porosity Porosity in CFM (ASTM D-3574, Test G). 
IFD 25% Indentation Force Deflection 25% (ASTM D-3574, 
Test B1 and Test B2). 
IFD 65% Indentation Force Deflection 65% (ASTM D-3574, 
Test B1 and Test B2). 
IFD 65/25 
Indentation Force Deflection 65% divided by 
Indentation Force Deflection, 25% (ASTM 
D-3574, Test B1 and Test B2). 
Tensile Tensile in psi (ASTM D-3574, Test E). 
Elongation 
Elongation in percent (ASTM D-3574, Test E). 
Tear Tear Resistance in pounds per inch (ASTM 
D-3574, Test F) 
Viscosity 
Viscosities were measured by Cannon Fenske 
viscometer (cSt). 
Filtration 
Filterability is determined by diluting one 
Hindrance 
part by weight sample (e.g., 200 grams) of 
(Filterability) 
polymer/polyol with two parts by weight 
anhydrous isopropanol (e.g., 400 grams) to 
remove any viscosity-imposed limitations 
and using a fixed quantity of material in 
relation to a fixed cross-sectional area of 
screen (e.g., 11/8 in. diameter), 
such that all of the polymer/polyol and 
isopropanol solution passes by gravity 
through a 150-mesh or 700-mesh screen. 
The 150-mesh screen has a square mesh 
with average mesh opening of 105 microns, 
and it is a "Standard Tyler" 150 
square-mesh screen. The 700-mesh screen 
is made with a Dutch twill weave. The actual 
screen used had a nominal opening of 30 
microns. The amount of sample which passes 
through the screen within 1200 seconds is 
reported in percent, a value of 100 percent 
indicates that over 99 weight percent 
passes through the screen. 
______________________________________ 
PREATIONS 
A. Preparation of Precursor (I) 
The following general procedure was followed for Example 1. The polyol was 
charged to a stirred reactor purged with nitrogen. The mixture was heated 
at 80.degree. C. followed by the addition of the maleic anhydride solid 
and 50.degree. C. aqueous KOH. The content were then heated to the desired 
temperature and ethylene oxide was added by pumping. After the reaction 
was completed, the excess oxide was removed by stripping under vacuum. The 
results are summarized in Table I below. The acid number reported was the 
final acid number (in mg KOH per gram of sample) after the product was 
stripped. 
B. Coupling of Precursor (I) 
The following general procedure was used in Example 2 for the reaction of 
Isocyanate A with the macromonomer formed in Example 1. The sample from 
Example 1 was placed in a stirred reactor and heated to 80.degree. C. The 
indicated amount of Isocyanate A was added slowly. The mixture was 
maintained at 80.degree. C. for one hour after the addition was complete. 
The results of these experiments are summarized in Table II. 
C. Preparation of High Potency Preformed Stabilizer (II) 
The preformed dispersion stabilizers were prepared in a continuous 
polymerization system 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 contents of the reactor were 
well mixed. The internal temperature of the reactor was controlled to 
within 1.degree. C. The product then flowed out the top of the second 
reactor continuously through a back pressure regulator that had been 
adjusted to maintain at least 65 psig pressure on both reactors. The 
preformed dispersion stabilizer then flowed through a cooler into a 
collection container. About 25 ppm of tertiary butyl catechol was added to 
the product container to prevent any polymerization during storage or 
transfer. 
D. Enhanced Polymer Polyols Preparations 
A continuous polymerizations 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 1.degree. C. 
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.degree. C. The product then flowed out the top of the second 
reactor continuously through a back pressure regulator that had been 
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 in the Examples were stable compositions. 
E. Free-rise Foam Preparations 
Examples 11 through 17 are free-rise foams prepared from the 
polymer/polyols as identified in the examples by the following procedure 
using the proportion of components shown in Table V, infra. The 
polymer/polyol, amine catalyst, and silicone surfactant were charged to a 
one-half gallon paper container equipped with a baffle assembly, and mixed 
at 2400 rpm for 60 seconds with a dual turbine stirrer placed about one 
inch above the bottom of the container. The mixture was allowed to set for 
15 seconds to degas. The tin catalyst was added after degassing and mixed 
at 2400 rpm's for 10 seconds. With the mixer still running, tolylene 
diisocyanate isomeric mixture was added, and the components were mixed for 
5 seconds. The mixture was poured after it started to cream into a 
14.times.14.times.6 inch carboard cake box. The foam mixture was allowed 
to react and subsequently to rise freely in the box until the reaction was 
complete. The foam was then placed in a conventional oven preheated to 
225.degree. C. for 5 minutes. Foam properties were determined pursuant to 
ASTM Standard D-3574-77. All of the foams were prepared using TDI at an 
index of 115. 
EXAMPLE 1 
This Example illustrates the preparation of a precursor (I) with fumarate 
type unsaturation. The process used was the same as has been previously 
set forth and the parameters are set forth in Table 1 below. 
TABLE I 
______________________________________ 
Example Number 1 
Polyol A 
Maleic Anhydride 
1.07 
Weight % 
meq/g 0.11 
KOH ppm 60 
Moles Ethylene 1.5 
Oxide per mole 
maleic anyhdride 
Reaction Temp., .degree.C. 
110 
Reaction 27 
Time (hours) 
Acid No. 0.39 
Isomerized Yes 
with morpholine 
Unsaturation, 0.090 (measured 
mequiv./g-polyol 
as fumarate) 
Viscosity 2452 
Retained 82 
Unsaturation (%) 
______________________________________ 
EXAMPLE 2 
This Example illustrates the coupling of a precursor (I) with an organic 
diisocyanate to a higher viscosity. The process used was the same as has 
been previously set forth and the parameters are set forth in Table II 
below. 
TABLE II 
______________________________________ 
Wt % Viscosity 
Isocyanate A cSt at 25.degree. C. 
______________________________________ 
0.64 6310 
______________________________________ 
EXAMPLE 3 
This Example illustrates the preparation of a stabilizer (II) as previously 
described. The specific parameters are set forth in Table III below. 
TABLE III 
______________________________________ 
Stabilizer (II) Preparation 
______________________________________ 
Feed Composition: 
Diluent Type Isopropanol/Polyol B 
Diluent Concentration, Wt. % in 
60%/3.99% 
Total Feed 
Precursor (I) Type From Ex. 2 
Precursor Concentration, Wt. % in 
19.95% 
Total Feed 
Monomers (30/70 A/S) 
15.96% 
Cat. conc. wt. %* 0.10% 
______________________________________ 
Reaction Conditions: 
Temperature, .degree.C. 
120 
Pressure, psig 65 
Residence Time in each stage, min. 
40 
______________________________________ 
*Solution of 50% tertiary butyl peroctoate in dioctyl phthalate. 
EXAMPLES 4-10 
The following examples show that polymer polyols made by this invention at 
polymer contents of about 45 percent and higher have both acceptable 
filtration hindrance and viscosity as compared to the prior art Example 
199 of U.S. Pat. No. 4,242,249 ("'249"). 
TABLE IV 
__________________________________________________________________________ 
Polymer Polyol Examples 
Example No. 4 5 6 7 8 9 10 199 (`249) 
__________________________________________________________________________ 
Polyol Type C C C C C D C V of `249 
Preparation Conditions: 
Reaction Temperature, .degree.C. 
115 115 115 116 114 115 115 125 
AZO conc., wt. % in total feed 
0.5 0.5 0.5 0.5 0.5 0.45 
(1) 1.3 
Stabilizer (II), 
5.2 5.2 5.9 5.9 7.2 5.1 5.1 4.4 
wt. % in total feed 
Stabilizer (II) 3 3 3 3 3 3 3 
of Example 
Isopropanol, wt. % in total feed 
4.0 3.1 3.5 3.5 4.3 5.0 4.0 
Monomer, wt. % in total feed 
43.2 
43.7 
48.1 
53.0 57.1 42.8 
43.2 
47.1 
Ratio of Acrylonitrile to 
30/70 
30/70 
30/70 
30/70 
30/70 
40/60 
30/70 
40/60 
Styrene, wt. % 
Residual Acrylonitrile, wt. % 
0.4 0.4 0.5 0.4 0.8 1.2 0.6 1.03 
Residual Styrene, m wt. % 
0.8 1.0 0.9 0.9 1.5 0.4 1.2 0.95 
Total Polymer in Product, 
45.2 
45.1 
50.2 
55.3 59.9 45.0 
44.9 
45.2 
by calc. wt. % 
Product Properties: 
Viscosity 3792 
4214 
5923 
10107 
13176 
6716 
3937 
35,500 
Filtration Hindrance: 
100 100 100 100 100 100 100 5.8 
% thru 150 mesh screen 
ppm on 150 mesh screen 
14 6 9 9 20 7 12 2374 
% thru 700 mesh screen 
100 100 100 40 19 100 100 0.335 
__________________________________________________________________________ 
(1) 0.70 weight % didecanoyl peroxide. 
EXAMPLE 11-17 
These examples (see Table V) show the higher loads, as indicated by the IFD 
numbers, that result from the higher polymer contents without any 
significant loss in tensile properties. 
TABLE V 
__________________________________________________________________________ 
Example Number 
POLYMER POLYOL 11 12 13 14 15 16 17 
__________________________________________________________________________ 
Polymer Polyol from 
Ex. 4 
Ex. 4 
Ex. 5 
Ex. 6 
Ex. 6 
Ex. 7 
Ex. 8 
FOAM FORMULATIONS 
(parts per hundred parts polyol) 
Polymer Polyol of Ex. 
100 100 100 100 100 100 100 
Water 2.3 2.3 2.3 2.3 2.3 2.3 2.3 
Catalyst A 0.03 0.03 0.03 0.03 0.03 0.03 0.03 
Catalyst B 0.11 0.11 0.11 0.11 0.11 0.11 0.11 
Surfactant A 0.70 0.70 0.70 0.70 0.70 0.70 0.70 
FOAM DATA 
Properties 
Density 2.34 2.33 2.43 2.36 2.34 2.37 2.38 
Porosity 34.7 34.7 40.1 32.0 37.4 15.8 21.2 
IFD, 25% 144.5 
140 153.9 
165 160.3 
212.9 
219.9 
65% 309.3 
301 336.8 
378.8 
364.8 
542.3 
572.3 
65/25 2.14 2.15 2.19 2.30 2.28 2.55 2.60 
Tensile 34.3 32.0 32.7 36.3 35.1 29.9 37.2 
Elongation 113.4 
115.8 
94.7 96.2 93.2 47.7 55.4 
Tear 2.07 2.34 2.10 2.39 2.63 2.0 2.04 
__________________________________________________________________________ 
Previously available polymer polyols having polymer contents of about 40 
percent can be converted into foam using the above formulation which have 
load-bearing capacities of about 120 lbs. as measured by their 25% IFD 
values. By contrast, the above examples demonstrate foams prepared from 
polymer/polyols of this invention have significantly higher load-bearing 
capacities. The patent literature does not appear to disclose foams having 
25% IFD values above 125 lbs. (see for example, U.S. Pat. Nos. 4,454,255; 
4,458,038; and 4,689,354).