Elastomer based on crude diphenylmethane diisocyanate and aniline in the RIM process

A RIM polyurethane elastomer prepared by reacting an organic polyisocyanate, a polyoxyalkylene polyether polyol, and a chain extender in the presence of an effective amount of aniline. Improvements in tensile and tear strength are realized.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to the preparation of reaction injection molded 
(RIM) polyurethane elastomer. It more particularly relates to the 
preparation of reaction injection molded polyurethane elastomers which 
have improved elongation and tear strength characteristics. 
2. Description of the Prior Art 
The automotive industry is faced with legislative mandates which require 
continued improved fuel economy. 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 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. 
The reaction injection molded polyurethanes of the instant invention are 
generally prepared by reacting a mixture of polyoxyalkylene polyether 
polyol with various polyisocyanates and incorporating therein chain 
extenders such as ethylene glycol and/or butanediol while maintaining a 
low free water content prior to annealing of the elastomer. 
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, recognizes that addition of minor amounts 
of aniline will result in improved physical properties when the 
polyisocyanate is crude MDI. 
SUMMARY OF THE INVENTION 
This invention comprises reaction injection molded (RIM) polyurethane 
elastomers having improved thermal dimensionally stable characteristics 
comprising the reaction product of an organic polyisocyanate (crude MDI), 
a polyoxyalkylene polyether polyol, and a chain extender and employing 
effective amounts of aniline as an additive.

DETAILED DESCRIPTION OF THE INVENTION 
Polyurethane compositions used in making reaction injection molded 
polyurethane elastomers are prepared in the usual manner using 
conventional techniques. 
The invention comprises reacting crude diphenylmethane diisocyanate with a 
polyether polyol, a chain extender, and an effective amount of aniline. 
This amount of aniline ranges from about 1 to about 12 parts of aniline 
per 100 parts of polyol. 
The chain extending agent may be chosen from a wide variety of chain 
extenders which include ethylene glycol, propylene glycol, 1,4-butanediol, 
glycerine, amino alcohols or mixtures thereof. The preferred chain 
extenders are ethylene glycol and butanediol. The concentration of chain 
extender may range from 10 percent to 30 percent based on the total weight 
of polyol and chain extender. The preferred range is from 15 percent to 25 
percent based on the total weight of polyol and chain extender. The 
concentration of polyol would thus range from 90 percent to 70 percent, 
preferably from 85 percent to 75 percent based on the total weight of 
polyol and chain extender. 
Representative polyols which may be employed in the RIM process 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. 
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. 
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. Pat. No. Re. 28,715 and unsaturated polyols such as those described 
in U.S. Pat. No. 3,652,659 and No. Re.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. 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. 
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(.beta.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-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, dimethyl 
.alpha.,.alpha.'-azo-bis(isobutyronitrile), 4,4'-azo-bis(4-cyanopetanoic) 
acid, azo-bis(isobutyronitrile), 1-t-amylazo-1-cyanocyclohexane, 
2-t-butylazo-2-cyano-4-methoxy-4-methylpentane, 
2-t-butylazo-2-cyano-4-methylpentane, 2-(t-butylazo)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. 
The RIM elastomers are generally prepared by the reaction of a 
polyoxyalkylene polyether polyol with an organic polyisocyanate 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. Pat. No. Re. 24,514 together with suitable machinery to be used in 
conjunction therewith. It is also possible to proceed with the preparation 
of the polyurethane elastomers by a prepolymer technique wherein an excess 
of organic polyisocyanate is reacted in a first step with the polyol to 
prepare a prepolymer having free isocyanate groups which is then reacted 
in a second step with more polyol. Alternately, the components may be 
reacted in a single working step commonly known as the "one-shot" 
technique of preparing polyurethanes. 
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'-di-methyldiphenylmethane-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 polyisocyanates are preferably 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 producing polyurethane elastomers in the 
present invention. 
Catalysts that are useful 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; 
D. 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 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 
having a molecular weight of about 5100, a hydroxyl number of 25 and 
containing 15 percent ethylene oxide. 
Polyol B--is a propylene oxide-ethylene oxide adduct of propylene glycol 
having a molecular weight of 3800, a hydroxyl number of 26, and containing 
20 percent ethylene oxide. 
Polyol C--is a propylene oxide-ethylene oxide adduct of glycerine and 
propylene glycol having a hydroxyl number of 33 containing 15 percent 
ethylene oxide, reacted with allyl glycidyl ether to contain 0.3 moles of 
unsaturation per mole of polyol and further reacted with 20 percent 2:3 
acrylonitrile:styrene monomer resulting in a hydroxyl number of 26. 
Catalyst A--is dibutyl tin dilaurate. 
Isocyanate A--is a crude diphenylmethane diisocyanate sold by Upjohn 
Corporation under the name Isonate 191. 
TABLE I 
______________________________________ 
Example 1 2 3 4 
______________________________________ 
Formulation, pbw 
Polyol A 65 65 65 65 
Polyol B 30 30 30 30 
Polyol C 5 5 5 5 
1,4-butanediol 
25 25 25 25 
Aniline -- 2 4 6 
T-12 Catalyst 
0.075 0.075 0.075 0.075 
Isocyanate A/100R 
70.0 71.3 72.7 73.9 
Index 105 105 105 105 
Physical Properties* 
Density, pcf 64.4 66.0 64.8 65.0 
100% Modulus, psi 
-- -- -- 2315 
Tensile Strength, psi 
1960 2395 2280 2415 
Elongation, % 
35 70 95 110 
Hardness (Shore D) 
50-48 54-50 55-50 56-53 
Split Tear, pi 
95 161 170 213 
Graves Tear, pi 
392 485 506 544 
Flex Recovery 
16/10 20/12 20/15 25/15 
Heat Sag, in., at 
0.33 0.46 0.64 0.63 
250.degree. F. 
Tangential Modulus, 
50.5 70.8 84.2 104.1 
K psi, -20.degree. F. 
72.degree. F. 
27.8 35.6 40.1 45.6 
158.degree. F. 
7.7 8.0 7.7 8.9 
Ratio -20.degree. F./158.degree. F. 
6.6 8.8 10.9 11.7 
______________________________________ 
*Post cured 45 minutes at 250.degree. F. 
TABLE II 
______________________________________ 
Example 5 6 7 8 9 
______________________________________ 
Formulation, pbw 
Polyol B 100 -- -- -- -- 
Ethylene Glycol 
15 -- -- -- -- 
Aniline -- 2 4 6 8 
T-12 Catalyst 
0.075 -- -- -- -- 
Isocyanate A/100R 
67.0 68.5 70.0 71.4 72.8 
Index 105 -- -- -- -- 
Physical Properties* 
Density, pcf 64.2 64.7 65.9 67.7 65.9 
100% Modulus, psi 
1693 1603 1700 1603 1590 
Tensile Strength, psi 
1993 2053 1910 1727 1660 
Elongation, % 
120 180 157 147 133 
Hardness (Shore D) 
44/44 49/46 51/49 52/50 50/48 
Split Tear, pi 
121 183 218 203 197 
Graves Tear, pi 
399 435 433 429 410 
Flex Recovery 
11/9 14/8 18/11 21/14 25/17 
Heat Sag, in., at 
0.38 0.48 0.55 0.47 0.31 
250.degree. F. 
Tangential Modulus, 
K psi, 
-20.degree. F. 
37.8 54.7 73.2 79.4 92.0 
72.degree. F. 
14.6 15.4 20.8 24.1 32.0 
158.degree. F. 
6.7 5.6 6.6 8.1 12.3 
Ratio -20.degree. F./158.degree. F. 
5.61 9.76 11.09 9.81 7.48 
______________________________________ 
*Post cured 45 minutes at 250.degree. F. 
TABLE III 
__________________________________________________________________________ 
Example 10 11 12 13 14 15 16 17 
__________________________________________________________________________ 
Formulation, pbw 
Polyol A 100 100 100 100 100 100 100 100 
1,4-butanediol 
24 18 21 21 24 21 18 21 
Aniline 6 2 1 4 2 8 6 2 
T-12 Catalyst 
0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 
Isocyanate A/100R 
72.0 
56.5 
62.3 
64.6 
69.3 
67.4 
59.8 
63.1 
Index 105 105 105 105 105 105 105 105 
Physical Properties* 
Density, pcf 61.8 
60.9 
60.6 61.2 
100% Modulus, psi 
1957 
1343 
-- 1700 
-- 1513 
1297 
-- 
Tensile Strength, psi 
2027 
1490 
1770 
1963 
1897 
1680 
1543 
1743 
Elongation, % 
113 117 90 140 83 143 170 97 
Hardness (Shore D) 
52-49 
44-39 
47-43 
49-42 
49-45 
48-44 
44-40 
47-43 
Split Tear, pi 
219 103 110 183 141 221 187 129 
Graves Tear, pi 
431 278 317 373 368 365 319 339 
Flex Recovery 
18/8 
13/5 
14/7 
15/8 
14/7 
20/12 
16/9 
12/5 
Heat Sag, in., at 250.degree. F. 
0.48 
0.53 
0.41 
0.49 
0.38 
0.45 
0.45 
0.45 
Tangential Modulus, K psi, 
-20.degree. F. 
97.3 
40.2 
57.0 
82.8 
88.8 
90.5 
60.3 
65.0 
72.degree. F. 
28.4 
9.2 15.1 
17.3 
23.0 
22.7 
13.5 
15.0 
158.degree. F. 
9.8 4.5 5.4 6.1 7.9 8.0 5.3 5.8 
Ratio -20.degree. F./158.degree. F. 
9.93 
8.93 
10.56 
13.65 
11.24 
11.36 
11.45 
11.21 
__________________________________________________________________________ 
*Post cured 45 minutes at 250.degree. F. 
TABLE IV 
__________________________________________________________________________ 
Example 18 19 20 21 22 23 24 25 26 27 28 
__________________________________________________________________________ 
Formulation, pbw 
Polyol B 100 100 100 100 100 100 100 100 100 100 100 
Ethylene Glycol 
18 12 12 18 16.5 
18 18 18 15 13.5 
18 
Aniline 2 6 3 9 4.5 3 6 1 6 7.5 12 
T-12 Catalyst 
0.075 
0.075 
0.075 
0.075 
0.075 
0.075 
0.075 
0.075 
0.075 
0.075 
0.075 
Isocyanate Al/100R 
78.5 
61.3 
58.8 
82.8 
75.3 
79.2 
81.1 
77.9 
71.4 
67.5 
84.5 
Index 105 105 105 105 105 105 105 105 105 105 105 
Physical Properties* 
Density, pcf 60.1 
59.8 
59.7 
60.6 
60.3 
60.7 
60.9 
60.3 
59.8 
60.1 
61.9 
100% Modulus, psi 
-- 973 1047 
-- 1550 
1757 
1703 
-- 1310 
1140 
-- 
Tensile Strength, psi 
1920 
1140 
1443 
1667 
1750 
1950 
1800 
1937 
1447 
1210 
1450 
Elongation, % 
100 180 207 70 153 113 123 100 153 153 nil 
Hardness (Shore D) 
45-42 
38-32 
37-31 
51-46 
47-41 
48-43 
51-47 
45-41 
44-39 
43-39 
54-49 
Split Tear, pi 
145 165 123 117 223 153 197 172 175 173 (b) 
Graves Tear, pi 
373 247 262 333 340 353 364 348 299 270 235 
Flex Recovery 
17/11 
16/11 
10/6 
30/19 
16/10 
16/9 
21/14 
17/8 
19/12 
20/14 
30/22 
Heat Sag, in., at 250.degree. F. 
0.35 
0.68 
0.75 
0.29 
0.41 
0.51 
0.29 
0.28 
0.33 
0.34 
0.22 
Tangential Modulus, K psi, 
-20.degree. F. 
55.8 
40.3 
23.5 
98.5 
63.0 
63.0 
82.0 
53.7 
63.3 
61.1 
116.3 
72.degree. F. 
15.7 
9.0 5.4 31.7 
13.7 
16.9 
23.4 
17.6 
17.0 
17.8 
42.7 
158.degree. F. 
7.6 4.5 2.8 14.4 
7.3 8.3 11.5 
8.9 8.0 9.1 22.3 
Ratio -20.degree. F./158.degree. F. 
7.3 8.90 
8.40 
6.83 
8.59 
7.56 
7.15 
6.06 
7.95 
6.72 
5.22 
__________________________________________________________________________ 
*Post cured 45 minutes at 250.degree. F. 
The data in the tables shows improvement in tensile strength, tear strength 
and room temperature tangential modulus when employing the products of the 
invention.