Process for reinforced reaction injection molding of polyurethanes

A reinforced reaction injection molding of polyurethanes is prepared by reacting an organic polyisocyanate, a polyoxyalkylene polyether polyol, a chain extending agent, a catalyst, optionally a blowing agent and glass fibers. The glass fibers form a stabilized dispersion in the polyol by employing as a suspending agent the reaction product of a polyamine and a polyester.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to the process for the preparation of reinforced 
reaction injection molded polyurethane foams. It more particularly relates 
to the process for the preparation of reinforced reaction injection molded 
polyurethane foams employing stabilized milled glass fiber dispersions in 
polyoxyethylene polyether polyol. 
2. Description of the Prior Art 
The automotive industry is faced with legislative mandates which require 
improved fuel economy standards. In order to achieve these higher fuel 
economy goals, the automotive industry has downsized large vehicles. 
Furthermore, the automotive industry has investigated the use of lower 
weight materials. Among the types of materials which may be employed are 
those produced by reinforced reaction injection molded polyurethanes. In 
order for these products to meet the demanding requirements for their 
application, they must be sufficiently rigid to be self supporting, have 
thermal dimensional stability to allow for normal processing operations at 
elevated temperatures, have low coefficients of thermal expansion, have a 
class A surface and good paintability, and enjoy good impact 
characteristics at low temperatures. Low coefficients of thermal expansion 
may be improved by the addition of milled glass fibers to the polyurethane 
matrix. Further, in order to enjoy the required thermal dimensional 
stability to allow the processor to, for example, paint at elevated 
temperatures, the urethane products must pass a heat sag test in the 
neighborhood of 165.degree. C. in order to be practical for use in the 
painting applications as practiced by the automotive industry. 
The reinforced reaction injection molded polyurethanes of the instant 
invention are generally prepared by reacting a mixture of polyoxyalkylene 
polyether polyol with various polyisocyanates and incorporating in the 
polyol component milled glass fibers in the presence of a wetting agent 
which promotes a stable dispersion of the glass fibers in the polyol. 
U.S. Pat. No. 3,892,691 teaches the preparation of polyurethane products 
employing quasi prepolymers of diphenylmethanediisocyanate and dipropylene 
glycols together with a polypropylene ether triol such as is prepared by 
the reaction of ethylene and propylene oxide with trimethylolpropane or 
glycerol and the use of the chain extender 1,4-butanediol. 
U.S. Pat. No. 4,243,760 teaches the preparation of reaction injection 
molded polyurethane products by employing chain extending agents such as 
ethylene glycol, propylene glycol and 1,4-butanediol. 
U.S. Pat. No. 4,102,833 also teaches the preparation of reaction injection 
molded urethanes by employing long chain polyols together with a short 
chain diol or triol such as ethylene glycol or glycerol. 
None of the prior art, however, discloses the utility of employing a 
wetting agent suitable for forming a stabilized dispersion of glass fibers 
in polyols for the preparation of reinforced reaction injection molded 
microcellular foams. 
SUMMARY OF THE INVENTION 
This invention comprises a process for the preparation of reinforced 
reaction injection molded (RRIM) polyurethane microcellular foams 
comprising the reaction product of an organic polyisocyanate, 
polyoxyalkylene polyether polyol, catalysts, chain extending agents, 
optionally a blowing agent, and a stabilized dispersion of milled glass 
fibers in the polyol employing as a suspending agent the reaction product 
of a polyester and a polyamine sold under the trademark BYK-W980 by 
BYK-Mallinckrodt Chemical Produkte GmBH. 
DETAILED DESCRIPTION OF THE INVENTION 
Polyurethane compositions used in making reinforced reaction injection 
molded polyurethane microcellular foams are prepared in the usual manner 
using conventional techniques. It is further well known that microcellular 
products must be cured at temperatures ranging from 250.degree. F. to 
350.degree. F. to have the desired improved physical properties of thermal 
dimensional stability. The microcellular product of the instant invention 
is prepared employing reaction products which contain dispersed therein, 
milled glass fibers having a filament length ranging from about 0.01 mm to 
about 10 mm and a diameter ranging from 0.005 to about 0.1 mm. The 
suspending agent employed is sold under the trademark BYK-W980 as 
disclosed above. The concentrations of suspending agent employed are those 
which effectively form a stable dispersion of glass fibers in either the 
polyol component the resin mixture or the isocyanate component, preferably 
in the polyol component. This is dependent upon the concentration range of 
glass fiber employed. The concentration of wetting agent may be from 0.01 
part to 1.0 part per 100 parts of polyol. The concentration of glass fiber 
in the final foam product ranges from about 5 percent to about 50 percent 
based on the weight of the foam. 
The compound BYK-W980 is reputedly the reaction product of a polyester and 
a polyamine, having a molecular weight of about 1000. The specific gravity 
20/4.degree. C. of the product is 0.99 and has 80 percent active 
ingredients with the remainder butyl cellosolve solvent. The elemental 
analysis of the product shows it to be 67.6 percent carbon, 10.7 percent 
hydrogen, 2.3 percent nitrogen and 19.3 percent oxygen. The product and 
process for the preparation of BYK-W980 are disclosed in German Patent No. 
1,157,326 which disclosure is incorporated herein by reference. 
The heat sag test employed was according to ASTM D-3769-79. This test 
employs a 4 mm thick specimen with a 100 mm overhang at a temperature of 
125.degree. C. for 60 minutes. Modifications of this test may also be 
employed using a 150 mm overhanging specimen. 
Although any polyoxyalkylene polyether polyols may be employed, the 
preferred high molecular weight polyether polyols are those which contain 
grafted therein vinylic monomers. 
The polyols which have incorporated therein the vinylic polymers may be 
prepared (1) by the in situ free-radical polymerization of an 
ethylenically unsaturated monomer or mixture of monomers in a polyol, or 
(2) by dispersion in a polyol of a preformed graft polymer prepared by 
free-radical polymerization in a solvent such as described in U.S. Pat. 
Nos. 3,931,092, 4,014,846, 4,093,573, and 4,122,056, the disclosures of 
which are herein incorporated by reference, or (3) by low temperature 
polymerization in the presence of chain transfer agents. These 
polymerizations may be carried out at a temperature between 65.degree. C. 
and 170.degree. C., preferably between 75.degree. C. and 135.degree. C. 
The amount of ethylenically unsaturated monomer employed in the 
polymerization reaction is generally from one percent to 60 percent, 
preferably from 10 percent to 40 percent, based on the total weight of the 
product. The polymerization occurs at a temperature between about 
80.degree. C. and 170.degree. C., preferably from 75.degree. C. to 
135.degree. C. 
The polyols which may be employed in the preparation of the graft polymer 
dispersions are well known in the art. Both conventional polyols 
essentially free from ethylenic unsaturation such as those described in 
U.S. Reissue Pat. No. 28,715 and unsaturated polyols such as those 
described in U.S. Pat. Nos. 3,652,659 and Reissue 29,014 may be employed 
in preparing the graft polymer dispersions used in the instant invention, 
the disclosures of which are incorporated by reference. Representative 
polyols essentially free from ethylenic unsaturation which may be employed 
are well known in the art. They are often prepared by the catalytic 
condensation of an alkylene oxide or mixture of alkylene oxides either 
simultaneously or sequentially with an organic compound having at least 
two active hydrogen atoms such as evidenced by U.S. Pat. Nos. 1,922,459; 
3,190,927, and 3,346,557, the disclosures of which are incorporated by 
reference. 
Representative polyols include polyhydroxyl-containing polyesters, 
polyoxyalkylene polyether polyols, polyhydroxy-terminated polyurethane 
polymers, polyhydroxyl-containing phosphorus compounds, and alkylene oxide 
adducts of polyhydric sulfur-containing esters, polyacetals, aliphatic 
polyols and thiols, ammonia, and amines including aromatic, aliphatic, and 
heterocyclic amines, as well as mixtures thereof. Alkylene oxide adducts 
of compounds which contain two or more different groups within the 
above-defined classes may also be used such as amino alcohols which 
contain an amino group and a hydroxyl group. Also, alkylene oxide adducts 
of compounds which contain one --SH group and one --OH group as well as 
those which contain an amino group and a --SH group may be used. 
Generally, the equivalent weight of the polyols will vary from 100 to 
10,000, preferably from 1000 to 3000. 
Any suitable hydroxy-terminated polyester may be used such as are obtained, 
for example, from polycarboxylic acids and polyhydric alcohols. Any 
suitable polycarboxylic acid may be used such as oxalic acid, malonic 
acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic 
acid, azelaic acid, sebacic acid, brassylic acid, thapsic acid, maleic 
acid, fumaric acid, glutaconic acid, .alpha.-hydromuconic acid, 
.beta.-hydromuconic acid, .alpha.-butyl-.alpha.-ethyl-glutaric acid, 
.alpha.,.beta.-diethylsuccinic acid, isophthalic acid, terephthalic acid, 
hemimellitic acid, and 1,4-cyclohexanedicarboxylic acid. Any suitable 
polyhydric alcohol may be used such as ethylene glycol, propylene glycol, 
trimethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 
1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 
1,7-heptanediol, glycerol, 1,1,1-trimethylolpropane, 
1,1,1-trimethylolethane, 1,2,6-hexanetriol, .alpha.-methyl glucoside, 
pentaerythritol, sorbitol and sucrose. Also included within the term 
"polyhydric alcohol" are compounds derived from phenol such as 
2,2'-bis(4,4'-hydroxyphenyl)propane, commonly known as Bisphenol A. 
Any suitable polyoxyalkylene polyether polyol may be used such as the 
polymerization product of an alkylene oxide or of an alkylene oxide with a 
polyhydric alcohol. Any suitable polyhydric alcohol may be used such as 
those disclosed above for use in the preparation of the hydroxy-terminated 
polyesters. Any suitable alkylene oxide may be used such as ethylene 
oxide, propylene oxide, butylene oxide, amylene oxide, and mixtures of 
these oxides. The polyalkylene polyether polyols may be prepared from 
other starting materials such as tetrahydrofuran and alkylene 
oxide-tetrahydrofuran mixtures; epihalohydrins such as epichlorohydrin; as 
well as aralkylene oxides such as styrene oxide. The polyoxyalkylene 
polyether polyols may have either primary or secondary hydroxyl groups. 
Included among the polyether polyols are polyoxyethylene glycol, 
polyoxypropylene glycol, polyoxybutylene glycol, polytetramethylene 
glycol, block copolymers, for example, combinations of polyoxypropylene 
and polyoxyethylene glycols, poly-1,2-oxybutylene and polyoxyethylene 
glycols, poly-1,4-tetramethylene and polyoxyethylene glycols, and 
copolymer glycols prepared from blends or sequential addition of two or 
more alkylene oxides. The polyoxyalkylene polyether polyols may be 
prepared by any known process such as, for example, the process disclosed 
by Wurtz in 1859 and Encyclopedia of Chemical Technology, Vol. 7, pp. 
257-262, published by Interscience Publishers, Inc. (1951) or in U.S. Pat. 
No. 1,922,459. Those preferred are the ethylene, propylene and butylene 
oxide adducts of ethylene glycol, propylene glycol, butylene glycol, 
glycerol, 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, 
1,2,6-hexanetriol, .alpha.-methyl-glucoside, pentaerythritol, sorbitol, 
2,2'-(4,4'-hydroxyphenyl)propane and sucrose, and mixtures thereof with 
equivalent weights from 100 to 5000. 
Suitable polyhydric polythioethers which may be condensed with alkylene 
oxides include the condensation product of thiodiglycol or the reaction 
product of a dicarboxylic acid such as is disclosed above for the 
preparation of the hydroxyl-containing polyesters with any other suitable 
thioether glycol. 
The hydroxyl-containing polyester may also be a polyester amide such as is 
obtained by including some amine or amino alcohol in the reactants for the 
preparation of the polyesters. Thus, polyester amides may be obtained by 
condensing an amino alcohol such as ethanolamine with the polycarboxylic 
acids set forth above or they may be made using the same components that 
make up the hydroxyl-containing polyester with only a portion of the 
components being a diamine such as ethylene diamine. 
Polyhydroxyl-containing phosphorus compounds which may be used include 
those compounds disclosed in U.S. Pat. No. 3,639,542. Preferred 
polyhydroxyl-containing phosphorus compounds are prepared from alkylene 
oxides and acids of phosphorus having a P.sub.2 O.sub.5 equivalency of 
from about 72 percent about 95 percent. 
Suitable polyacetals which may be condensed with alkylene oxides include 
the reaction product of formaldehyde or other suitable aldehyde with a 
dihydric alcohol or an alkylene oxide such as those disclosed above. 
Suitable aliphatic thiols which may be condensed with alkylene oxides 
include alkanethiols containing at least two -SH groups such as 
1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, and 
1,6-hexanedithiol; alkene thiols such as 2-butene-1,4-dithiol; and alkyne 
thiols such as 3-hexyne-1,6-dithiol. 
Suitable amines which may be condensed with alkylene oxides include 
aromatic amines such as aniline, o-chloroaniline, p-aminoaniline, 
1,5-diaminonaphthalene, methylenedianiline, the condensation products of 
aniline and formaldehyde, and 2,4-diaminotoluene; aliphatic amines such as 
methylamine, triisopropanolamine, ethylenediamine, 1,3-diaminopropane, 
1,3-diaminobutane, and 1,4-diaminobutane. 
Also, polyols containing ester groups can be employed in preparing the 
graft polymer dispersions. These polyols are prepared by the reaction of 
an alkylene oxide with an organic dicarboxylic acid anhydride and a 
compound containing reactive hydrogen atoms. A more comprehensive 
discussion of these polyols and their method of preparation can be found 
in U.S. Pat. Nos. 3,585,185; 3,639,541 and 3,639,542. 
The unsaturated polyols which may be employed for preparation of graft 
copolymer dispersions may be prepared by the reaction of any conventional 
polyol such as those described above with an organic compound having both 
ethylenic unsaturation and a hydroxyl, carboxyl, anhydride, isocyanate or 
epoxy group or they may be prepared by employing an organic compound 
having both ethylenic unsaturation and a hydroxyl, carboxyl, anhydride, or 
epoxy group as a reactant in the preparation of the conventional polyol. 
Representative of such organic compounds include unsaturated mono- and 
polycarboxylic acids and anhydrides such as maleic acid and anhydride, 
fumaric acid, crotonic acid and anhydride, propenyl succinic anhydride, 
and halogenated maleic acids and anhydrides, unsaturated polyhydric 
alcohols such as 2-butene-1,4-diol, glycerol allyl ether, 
trimethylolpropane allyl ether, pentaerythritol allyl ether, 
trimethylolpropane allyl ether, pentaerythritol allyl ether, 
pentaerythritol vinyl ether, pentaerythritol diallyl ether, and 
1-butene-3,4-diol, unsaturated epoxides such as 1-vinylcyclohexene 
monoxide, butadiene monoxide, vinyl glycidyl ether, glycidyl methacrylate 
and 3-allyloxypropylene oxide. 
As mentioned above, the graft polymer dispersions used in the invention are 
prepared by the in situ polymerization of an ethylenically unsaturated 
monomer or a mixture of ethylenically unsaturated monomers, either in a 
solvent or in the above-described polyols. Representative ethylenically 
unsaturated monomers which may be employed in the present invention 
include butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, 1,7-octadiene, 
styrene, .alpha.-methylstyrene, methylstyrene, 2,4-dimethylstyrene, 
ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, 
cyclohexylstyrene, benzylstyrene, and the like; substituted styrenes such 
as chlorostyrene, 2,5-dichlorostyrene, bromostyrene, fluorostyrene, 
trifluoromethylstyrene, iodostyrene, cyanostyrene, nitrostyrene, 
N,N-dimethylaminostyrene, acetoxystyrene, methyl-4-vinylbenzoate, 
phenoxystyrene, p-vinyldiphenyl sulfide, p-vinylphenyl phenyl oxide, and 
the like; the acrylic and substituted acrylic monomers such as 
acrylonitrile, acrylic acid, methacrylic acid, methylacrylate, 
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, methyl methacrylate, 
cyclohexyl methacrylate, benzyl methacrylate, isopropyl methacrylate, 
octyl methacrylate, methacrylonitrile, methyl .alpha.-chloroacrylate, 
ethyl .alpha.-ethoxyacrylate, methyl .alpha.-acetaminoacrylate, butyl 
acrylate, 2-ethylhexyl acrylate, phenyl acrylate, phenyl methacrylate, 
.alpha.-chloroacrylonitrile, methacrylonitrile, N,N-dimethylacrylamide, 
N,N-dibenzylacrylamide, N-butylacrylamide, methacryl formamide, and the 
like; the vinyl esters, vinyl ethers, vinyl ketones, etc., such as vinyl 
acetate, vinyl chloroacetate, vinyl alcohol, vinyl butyrate, isopropenyl 
acetate, vinyl formate, vinyl acrylate, vinyl methacrylate, vinyl 
methoxyacetate, vinyl benzoate, vinyl iodide, vinyltoluene, 
vinylnaphthalene, vinyl bromide, vinyl fluoride, vinylidene bromide, 
1-chloro-1-fluoroethylene, vinylidene fluoride, vinyl methyl ether, vinyl 
ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl 
ether, vinyl phenyl ether, vinyl 2-butoxyethyl ether, 
2,4-dihydro-1,2-pyran, 2-butoxy-2'-vinyloxy diethyl ether, vinyl 
2-ethylthioethyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl 
phenyl ketone, vinyl phosphonates such as bis(.alpha.-chloroethyl) 
vinylphosphonate, vinyl ethyl sulfide, vinyl ethyl sulfone, 
N-methyl-N-vinyl acetamide, N-vinylpyrrolidone, vinyl imidazole, divinyl 
sulfide, divinyl sulfoxide, divinyl sulfone, sodium vinylsulfonate, methyl 
vinylsulfonate, N-vinyl pyrrole, and the like; dimethyl fumarate, dimethyl 
maleate, maleic acid, crotonic acid, fumaric acid, itaconic acid, 
monomethyl itaconate, butylaminoethyl methacrylate, dimethylaminoethyl 
methacrylate, glycidyl acrylate, allyl alcohol, glycol monoesters of 
itaconic acid, dichlorobutadiene, vinyl pyridine, and the like. Any of the 
known polymerizable monomers can be used and the compounds listed above 
are illustrative and not restrictive of the monomers suitable for use in 
this invention. Preferably, the monomer is selected from the group 
consisting of acrylonitrile, styrene, methyl methacrylate and mixtures 
thereof. 
Illustrative initiators which may be employed for the polymerization of 
vinyl monomers are the well-known free radical types of vinyl 
polymerization initiators, for example, the peroxides, persulfates, 
perborates, percarbonates, azo compounds, etc., including hydrogen 
peroxide, dibenzoyl peroxide, acetyl peroxide, benzoyl hydroperoxide, 
t-butyl hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, butyryl 
peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, 
paramenthane hydroperoxide, di-.alpha.-cumyl peroxide, dipropyl peroxide, 
diisopropyl peroxide, isopropyl-t-butyl peroxide, butyl-t-butyl peroxide, 
difuroyl peroxide, ditriphenylmethyl peroxide, bis(p-methoxybenzoyl) 
peroxide, p-monomethoxybenzoyl peroxide, p-monoethoxybenzoyl peroxide, 
rubene peroxide, ascaridol, t-butyl peroxybenzoate, diethyl 
peroxyterephthalate, propyl hydroperoxide, isopropyl hydroperoxide, 
n-butyl hydroperoxide, t-butyl hydroperoxide, cyclohexyl hydroperoxide, 
trans-decalin hydroperoxide, .alpha.-methylbenzyl hydroperoxide, 
.alpha.-methyl-.alpha.-ethyl benzyl hydroperoxide, tetralin hydroperoxide, 
triphenylmethyl hydroperoxide, diphenylmethyl hydroperoxide, 
.alpha.-.alpha.'-azo-bis(2-methyl) butyronitrile, 
.alpha.,.alpha.'-azo-bis(2-methyl) heptonitrile, 
1,1'-azo-bis(1-cyclohexane) carbonitrile, 1,1'-azo-bis(cyclohexane 
carbonitrile), .alpha.,.alpha.'-azobis(isobutyrate), dimethyl 
.alpha.,.alpha.'-azo-bis(isobutyronitrile), 4,4'-azo-bis(4-cyanopetanoic) 
acid, 2,2'-azo-bis(isobutyronitrile), 1-t-amylazo-1-cyanocyclohexane, 
2,2'-azo-bis(2,4-dimethylvaleronitrile), 
2-t-butylazo-2-cyano-4-methoxy-4-methylpentane, 
2,2'-azo-bis-2-methylbutanenitrile, 2-t-butylazo-2-cyanobutane, 
1-t-amylazo-1-cyanocyclohexane, 
2,2'-azo-bis(2,4-dimethyl-4-methoxyvaleronitrile), 
2,2'-azo-bis-2-methylbutyronitrile, 1,1'-azo-bis-cyclohexane-carbonitrile, 
2-t-butylazo-2-cyano-4-methylpentane, 2-(t-butylazo)isobutyronitrile, 
2-t-butylazo-2-isobutyronitrile, 2-t-butylazo-2-cyanobutane, 
1-cyano-1-(t-butylazo)cyclohexane, t-butyl peroxy-2-ethylhexanoate, 
t-butylperpivalate, 2,5-dimethyl-hexane-2,5-diper-2-ethyl hexoate, 
t-butylperneo-decanoate, t-butylperbenzoate, t-butyl percrotonate, 
persuccinic acid, diisopropyl peroxydicarbonate, and the like; a mixture 
of initiators may also be used. Photochemically sensitive radical 
generators may also be employed. Generally, from about 0.5 percent to 
about 10 percent, preferably from about 1 percent to about 4 percent, by 
weight of initiator based on the weight of the monomer will be employed in 
the final polymerization. 
Stabilizers may be employed during the process of making the graft polymer 
dispersions. One such example is the stabilizer disclosed in U.S. Pat. No. 
4,148,840 which comprises a copolymer having a first portion composed of 
an ethylenically unsaturated monomer or mixture of such monomers and a 
second portion which is a propylene oxide polymer. Other stabilizers which 
may be employed are the alkylene oxide adducts of copolymers of 
styrene-allyl alcohol as disclosed in copending applications Ser. No. 
179,136, now U.S. Pat. No. 4,334,049 and Ser. No. 179,137, now U.S. Pat. 
No. 4,327,005. 
The conventional polyurethane foams employed in the present invention are 
generally prepared by the reaction of a polyoxyalkylene polyether polyol 
having a graft polymer content of at least 5 parts per 100 parts of polyol 
at least 3 parts by weight per 100 parts of polyol for high resiliency 
polyurethane foams with an organic polyisocyanate in the presence of a 
blowing agent and optionally in the presence of additional 
polyhydroxyl-containing components, chain-extending agents, catalysts, 
surface-active agents, stabilizers, dyes, fillers such as milled glass 
fibers and pigments. Suitable processes for the preparation of cellular 
polyurethane plastics are disclosed in U.S. Reissue Patent No. 24,514 
together with suitable machinery to be used in conjunction therewith. It 
is also possible to proceed with the preparation of the polyurethane 
plastics by a prepolymer technique wherein an excess of organic 
polyisocyanate is reacted in a first step with the polyol of the present 
invention to prepare a prepolymer having free isocyanate groups which is 
then reacted in a second step with a blowing agent to prepare a foam. 
Alternately, the components may be reacted in a single working step 
commonly known as the "one-shot" technique of preparing polyurethanes. Low 
boiling hydrocarbons such as pentane, hexane, heptane, pentene, and 
heptene; azo compounds such as azohexahydrobenzodinitrile; halogenated 
hydrocarbons such as dichlorodifluoromethane, trichlorofluoromethane, 
dichlorodifluoromethane, trichlorofluoromethane, dichlorodifluoroethane, 
vinylidene chloride, dichlorofluoromethane, dichloromethane, 
tricloromethane, dichlorofluoroethane, trichlorotrifluoromethane, 
hexafluorocyclobutane, and octafluorocyclobutane, may be used as blowing 
agents. 
The organic polyisocyanate employed in the instant invention corresponds to 
the formula R'(NCO)z wherein R' is a polyvalent organic radical which is 
either aliphatic, arylalkyl, alkylaryl, aromatic or mixtures thereof and z 
is an integer which corresponds to the valence of R' and is at least 2. 
Representative of the types of organic polyisocyanates contemplated herein 
include, for example, 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-diisocyanate-3-methoxyhexane, 
1,8-diisocyanatooctane, 1,5-diisocyanato-2,2,4-trimethylpentane, 
1,9-diisocyanatononane, 1,10-diisocyanatopropyl ether of 1,4-butylene 
glycol, 1,11-diisocyanatoundecane, 1,12-diisocyanatododecane, 
bis-(isocyanatohexyl)sulfide, 1,4-diisocyanatobenzene, 
1,3-diisocyanato-o-xylene, 1,3-diisocyanato-p-xylene, 
1,3-diisocyanato-m-xylene, 2,4-diisocyanato-1-chlorobenzene, 
2,4-diisocyanato-1-nitrobenzene, 2,5-diisocyanato-1-nitrobenzene, 
m-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene 
diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, 
1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 
1,4-cyclohexane diisocyanate, hexahydrotoluene diisocyanate, 
1,5-naphthylene diisocyanate, 1-methoxy-2,4-phenylene diisocyanate, 
4,4'-cyclohexane diisocyanate, hexahydrotoluene diisocyanate, 
1,5-naphthylene diisocyanate, 1-methoxy-2,4-phenylene diisocyanate, 
4,4'-diphenylmethane diisocyanate, 4,4'-biphenylene diisocyanate, 
3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 
3,3'-dimethyl-4,4'-diphenylmethane diisocyanate and 
3,3'-dimethyldiphenylmethane-4,4'-diisocyanate; the triisocyanates such as 
4,4',4"-triphenylmethane triisocyanate, polymethylene polyphenylene 
polyisocyanate and 2,4,6-toluene triisocyanatate; and the tetraisocyanates 
such as 4,4'-dimethyl-2,2'-5,5'-diphenylmethane tetraisocyanate. 
Especially useful due to their availability and properties are toluene 
diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane 
diisocyanate, polymethylene polyphenylene polyisocyanate, and mixtures 
thereof. 
These polyisocyanates are prepared by conventional methods known in the art 
such as the phosgenation of the corresponding organic amine. Included 
within the useable isocyanates are the modifications of the above 
isocyanates which contain carbodiimide, allophonate or isocyanurate 
structures. Quasi-prepolymers may also be employed in the process of the 
subject invention. These quasi-prepolymers are prepared by reacting an 
excess of organic polyisocyanate or mixtures thereof with a minor amount 
of an active hydrogen-containing compound a determined by the well-known 
Zerewitinoff test, as described by Kohler in Journal of the American 
Chemical Society, 49, 3181 (1927). These compounds and their methods of 
preparation are well known in the art. The use of any one specific active 
hydrogen compound is not critical hereto, rather any such compound can be 
employed herein. Generally, the quasi-prepolymers have a free isocyanate 
content of from 20 percent to 40 percent by weight. 
Crude polyisocyanate may also be used in the compositions of the present 
invention, such as crude toluene diisocyanate obtained by the phosgenation 
of a mixture of toluene diamines or crude polymethylene polyphenylene 
polyisocyanate obtained by the phosgenation of crude polymethylene 
polyphenylene polyamine. 
The graft polymer polyols may be employed along with another 
polyhydroxyl-containing component commonly employed in the art. Any of the 
polyhydroxyl-containing components which are described above for use in 
the preparation of the graft polyols may be employed in the preparation of 
the polyurethane foams useful in the present invention. 
Chain-extending agents which may be employed in the preparation of the 
polyurethane foams include those compounds having at least two functional 
groups bearing active hydrogen atoms such as water, hydrazine, primary and 
secondary diamines, amino alcohols, amino acids, hydroxy acids, glycols, 
or mixtures thereof. A preferred group of chain-extending agents includes 
water, ethylene glycol, 1,4-butanediol, and primary and secondary diamines 
which react more readily with the polyisocyanates than does water. These 
include phenylenediamine, ethylenediamine, diethylenetriamine, 
N-(2-hydroxypropyl)-ethylenediamine, 
N,N'-di(2-hydroxypropyl)ethylenediamine, piperazine, and 
2-methylpiperazine. 
Catalysts that are useful in producing resilient polyurethane foams in 
accordance with this invention include: 
A. tertiary amines such as triethylene diamine, bis(dimethylamino 
ethyl)ether, triethylamine, N-methylmorpholine, N-ethylmorpholine, 
N,N-dimethylbenzylamine, N,N-dimethylethanolamine, and the like; 
B. tertiary phosphines, such as, trialkyl phosphines, dialkyl benzyl 
phosphines, and the like; 
C. strong bases such as alkaline and alkali earth metal hydroxides, and 
phenoxides; 
acidic metal salts of strong acids such as ferric chloride, stannic 
chloride, stannous chloride, antimony trichloride, bismuth nitrate and 
chloride and the like; 
E. chelates of various metals such as those obtained from acetylacetone, 
benzoyl acetone, ethyl acetoacetate and the like; 
F. alcoholates and phenolates of various metals such as Ti(OR).sub.4, 
Sn(OR).sub.2, (Al(OR).sub.3, and the like wherein R is alkyl or aryl and 
the like; 
G. salts of organic acids with a variety of metals such as alkali metals, 
alkaline earth metals, Al, Sn, Mn, Pb, Co, Ni, and Cu, including, for 
example, sodium acetate, potassium laurate, calcium hexanoate, stannous 
acetate, stannous octoate, stannous oleate, lead octoate, metallic dryers 
such as manganese and cobalt naphthenates, and the like; 
H. organic metallic derivatives of tetravalent tin, trivalent and 
pentavalent arsenic, antimony and bismuth, and metal carbonyls of iron, 
cobalt and nickel. 
The process and product thereof of this invention are explained further by 
the following examples. The parts given in the examples are by weight 
unless otherwise indicated. The following abbreviations are employed in 
the examples: 
Polyol A is a propylene oxide ethylene oxide adduct of trimethylolpropane 
containing 13 percent ethylene oxide and having a hydroxyl number of 35. 
Polyol B is a graft polymer dispersion of 21 percent vinyl polymer content 
1:1 acrylonitrile:styrene prepared by the in situ polymerization of a 1:1 
weight mixture of acrylonitrile:styrene in a polyol which a propylene 
oxide, ethylene oxide and alkyl glycidyl ether adduct of a mixture of 
glycerine and propylene glycol containing a 14 percent ethylene oxide cap 
and having a hydroxyl number of 33. 
Isonate 181 is a urethane-modified diphenylmethane diisocyanate 
manufactured by Upjohn Chemical Corporation. 
Isonate 143L is a carbodiimide-modified diphenylmethane diisocyanate 
manufactured by Upjohn Chemical Corporation.