Non-elastomeric polyurethane compositions containing cyclic polyethers
United States Patent 1 Olstowski et a1.  
 1 1 NON-ELASTOMERIC POLYURETHANE COMPOSITIONS CONTAINING CYCLIC POLYETIIERS [75] Inventors: Franciszek Olstowski. Freeport;  
 Donald B. Parrish. Lake Jackson.  
 both of Tex.  
 [73] Assignee: The Dow Chemical Company,  
 Midland, Mich.  
 [22] Filed: Dec. 17, 1973 [21] Appl. No.: 425,398  
 Related U.S. Application Data [63] Continuation-in-part of Ser. No. 366.835. June 4, 1973. which is a continuation-in-part of Ser. No. 179.149. Sept. 9. 1971. abandoned.  
 [52] U.S. Cl. 260/30.4 N; 260/18 TN; 260/30.2; 260/30.6 R; 260/32.2; 250/332 R; 260/33.4  
 UR; 260/336 UB [51] Int. Cl... C08g 51/34; C08g 51/46; C08g 51/50 Field of Search.. 260/30.4 N, 45.8 A. 45.8 NZ, 260/DIG. 24. 45.8 SN. 30.2, 77.5 MA. 75  
 NP; 106/15 FP [56] References Cited UNITED STATES PATENTS 3.102.875 9/1963 Heiss 360/304 N 1 51 Apr. 22, 1975 3.148.167 9/1964 Keplinger 260/45.8 A 3.243.406 3/1966 Grccnbaum 260/4518 A 3.489.723 1/1970 Kraft 260/37 N 3.499.858 3/1970 Strassel 260/30.4 N 3.631.145 12/1971 Kerst 260/45.8 A 3.632.544 1/1972 Boyer 260/30.4 A 3.637.583 l/l972 Mctzgcr 260/45.8 A 3.770.693 11/1973 Mctzgcr 260/45.8 NZ  
 Primary Examiner-Joseph L. Schofer Assistant Examiner-Paul R. Michl Attorney. Agent. or Firm-James G. Carter [57] ABSTRACT 10 Claims, No Drawings NON-ELASTOMERIC POLYURETHANE COMPOSITIONS CONTAINING CYCLIC POLYETHERS This application is a continuation-in-part of our copending application Ser. No. 366,835, filed June 4, 1973 which is a continuation-in-part of application Ser. No. 179,149, filed Sept. 9, 1971 now abandoned.  
  This invention relates to polyurethane compositions and more particularly relates to rapid-setting, solid. dense, non-elastomeric polyurethane compositions.  
  Rapid setting, dense, opaque polyurethane compositions have been taught in US. Pat.No. 3,378,511. Such compositions employ, as one of the essential ingredients, a liquid plasticizer which is a dicarboxylic acid ester. These compositions while useful in many applications, have some disadvantages in that they are not readily paintable and are susceptible to degradation in such common solvents as acetone, methyl isobutylketone, methylene chloride, ethylene dichloride, ethyl acetate, tetrahydrofuran and the like.  
  The present invention provides one or more of the following advantages over the prior art, i.e. improved detail reproduction in ornamental castings having intricate detail, improved paintability, improved solvent resistance, improved lubricity in cast gears and other machine elements and the like.  
  It is an object of the present invention to provide a rapid-setting, dense, rigid polyurethane composition.  
  Another object of the present invention is to provide rapid-setting, non-elastomeric, opaque polyurethane compositions.  
  A further object of the present invention is to provide rapid-setting, dense, non-elastomeric, transparent polyurethane compositions. 1  
  These and other objects will become apparent from a reading of the following detailed specification.  
  The present invention concerns a composition which comprises a polyether polyol, an organic polyisocyanate and a non-amine-containing catalyst for urethane formation, characterized in that it contains a liquid modifier compound having a boiling point above about 150C. selected from the group consisting of hydroxylcontaining and non-hydroxyl-containing polyoxyalkylene compounds, ester-modified polyoxyalkylene compounds, fatty acids, naturally occurring fatty oils, organic phosphates, organic phosphites, organic phosphonates, cyclic ethers, non-ester-containing aromatic compounds, partially hydrogenated aromatic compounds, organic carbonate, halogenated aliphatic com pounds, cyclic sulfones and mixtures thereof.  
  All the liquid modifier compounds have at least two points in common. They are (I) an apparent ability to act as a heat sink to prevent excessive bubbling which would result from the heat generated by the exothermic heat of reaction and (2) they have boiling points at atmospheric pressure above about 150C.  
  The term non-elastomeric polyurethane as employed herein is defined as a polyurethane product having an elongation value of less than 80 percent and the term dense is defined as a density of at least about 1 gram/cc.  
 Non-elastomeric, rapid-setting, polyurethane compositions are obtained by intimately admixing together a composition comprising A. a polyether polyol whihc is the adduct of a polyhydric initiator compound having a functionality of from 3 to about 8 with a vicinal epoxy compound, said polyol having a hydroxyl equivalent weight of at least about and less than about 230;  
 B. an organic polyisocyanate;  
 C. a liquid modifier compound having a boiling point above about C at atmospheric pressure including for example hydroxyl-containing and non-hydroxyl-containing polyoxyalkylene compounds, fatty acids, naturally occurring fatty oils, organic phosphates, organic phosphites, organic phosphonates, cyclic ethers, nonester containing aromatic compounds, partially hydrogenated aromatic compounds, organic carbonates, halogenated aliphatic compounds, cyclic sulfones, and mixtures thereof in any combination, and  
 D. a non-amine containing catalyst for urethane formation;  
 and wherein Components (A) and (B) are present in amounts so as to provide an NCOzOH ratio of from about 0.8:1 to about 2:1 and preferably from about 0.95:1 to about 1.1:1; Component C is present in quantities of from about 20-50% and preferably from about 30-50% with the proviso that when component (B) is a prepolymer containing less than about 40% NCO groups by weight, then component (C) is present in quantities of from about 10% to about 50% by weight of the sum of Components (A), (B), and (C); and (D) is present in quantities of from about 0.2 to about 10%, preferably from about 0.2 to about 3%, and most preferably from about 0.5 to about 3% by weight of the sum of the weights of Components (A), (B) and (C); with the proviso that when Component (C) is a halogenated aliphatic compound, it is employed in a range of from about 0.2 to about 50 percent by weight of the sum of the weights of Components (A), (B) and (C); that when the halogenated aliphatic compound also contains hydroxyl groups and has an OH equivalent weight of less than about 500, it is employed in quantities of from about 0.2 to about 5 percent by weight based upon the sum of the weight of Components (A), (B) and (C), and that when Component (C) is a non-estercontaining aromatic compound or a halogenated aliphatic compound, the nonamine-containing catalyst, Component (D), is employed in quantities of from about 0.01 to about 10 percent by weight of the combined weights of Components (A), (B) and (C).  
  Suitable initiator compounds having from 3 to 8 hydroxyl groups which can be employed to prepare the polyols (Component A) employed in the present invention include, for example, glycerine, trimethylolpropane, pentaerythritol, sorbitol, sucrose, mixtures thereof and the like.  
  Suitable vicinal epoxy compounds which may be reacted with the initiator compounds to prepare the polyols employed as Component A in the present invention include, for example, the lower alkylene oxides and substituted alkylene oxides such as ethylene oxide, 1,2- propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, epichlorohydrin, epibromohydrin, epiodohydrin, styrene oxide, mixtures thereof and the like.  
  Suitable polyoxyalkylene compounds which may be employed as the liquid modifier compound (Component C) include, for example,  
 1. a liquid, totally-capped or non-hydroxylcontaining block or randomly formed polyoxyalkylene glycol represented by the general formula 3 4 phatic, a saturated or unsaturated cyclic aliphatic, or R i L aromatic polycarboxylic acid, halogenated derivatives j k thereof and mixtures thereof, each R is a substituent R2 :2 independently selected from hydrogen atoms, an alkyl 5 radical having from 1 to 20 carbon atoms, a halomethyl radical, a phenyl radical, and a phenoxymethyl radical, an alkoxymethyl radical with the priviso that one of the R substituents must be hydrogen, R is hydrogen or a saturated or unsaturated aliphatic group having from 1 to 20 carbon atoms, m has an average value of from about 1.0 to about 2.0, n has a value from about 1 to about 5, x has a value from about I to about 8 and y has a value of l or 2 and wherein said ester-modified polyether compound has a hydroxyl equivalent weight above about 500 when 3 or more hydroxyl groups are present and when 2 hydroxyl groups are present an average equivalent weight of above about 700 and when zero or one hydroxyl group is present a molecular weight of above about 700.  
  Suitable initiators which may be employed to prepare the general formula the liquid polyoxyalkylene and ester-modified polyoxy- (m alkylene modifier compounds (Component C) of the present invention include compounds having from 1 to R/OCH2CH\/OCHQ-CH .(OCHzCH OH about 8 hydroxyl groups such as, for example, metha- LA nol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, butylene glycol, 1,6-hexane diol, glycerine,  
 wherein R and R are independently selected from saturated and unsaturated hydrocarbon groups having from about 1 to about 6, preferably from about 1 to about 3, carbon atoms; R R and R are independently hydrogen, and aryl group, and alkyl group or haloalkyl group, said alkyl or haloalkyl group having from about l to about 2 carbon atoms with the proviso that when R R R,, is a haloalkyl group, it is present in minor amounts i.e. a ratio of from about 0 to about l0 percent of the total R R R groups, and 1&#39; x x, are integers. such that the boiling point of the liquid capped polyalkylene glycol is above about 150C;  
 2. a liquid partially capped, block or randomly formed polyoxyalkylene compound represented by wherein R and R R R are as defined in formula trimethylolpropane, pentaerythritol, sorbitol, sucrose,  
  1 above and x,, x x are integers, the sum of mixtures thereof and the like. which provides the partially capped polyoxyalkyl- When the liquid modifier compound, Component C, ene compound with a molecular weight of at least is an ester modified polyether polyol, the initiator combout 700; pound may also be and is preferably an adduct of the 3. a liquid, block or randomly formed polyoxyalkylabove mentioned initiator compounds and one or more ene glycol represented by the general formula of the following vicinal epoxide-containing com- (IH) HOCH2CH)/OOH2-CH\. .(OCHzCH OH 1 1) t\ I ia )2 1 )H wherein R R R, are as defined in formula I pounds, i.e. the initiator compound is a polyoxyalkylabove and x x x are integers, the sum of ene compound having 1 to 8 hydroxyl groups, preferawhich provides the polyoxyalkylene glycol with an 40 bly 2 to about 3 or 4 hydroxyl groups. equivalent weight of at least about 700, and Suitable vicinal epoxide compounds which may be 4. a liquid, random or block polyoxyalkylene polyol reacted with the above mentioned initiator compounds having a hydroxyl functionality of from 3 to about to prepare the modifier compounds (Component C) 8 represented by the general formula employed in the present invention include, for examwherein R R R, are as defined in formula I ple, ethylene oxide, 1,2-propylene oxide, 1,2-butylene above, Z is the residue of an initiator compound 0 oxide, 2,3-butylene oxide, epichlorohydrin, epihaving from 3 to about 8 hydroxyl groups, .n, x2. bromohydrin, epiodohydrin, styrene oxide, mixtures x are intergers, the sum of which provides the thereof and the like. polyoxyalkylene polyol with a hydroxyl equivalent The liquid modifier compounds represented by forweight of at least about 500 and q is an integer havmulae l-lV and methods for their preparation are well ing a value of from 3 to about 8. know in the art, e.g. U.S. Pat. N0. 2,448,664; US. Pat.  
  Suitable ester-modified polyoxyalkylene compounds No. 2,425,755; US. Pat. No. 2,782,240 and US. Pat. which may be employed as the liquid modifier com- No. 2,520,611. Methods for the preparation of the liqpound (Component C) include, for example, those liquid modifier compounds represented by the formula V uid ester-modified polyethers having a boiling point are given in a copending application Ser. No. 67,233, above about 150C represented by the general formula filed Aug. 26, 1970 by Robert W. McAda, Jr. for ES- TER-MODlFlED POLYETHER POLYOLS and in A O a Z a O /CH CH O\ U.S. Pat. NO. 3,502,601.  
 L \1 j Suitable non-ester contalnlng aromatic compounds R R Y which may be employed as the liquid modifier comwherein A is a residue of an initiator or starting compound having a boiling point above about l50C (Compound having from 1 to about 8 hydroxyl groups, Z is ponent C) in the present invention include, for examthe residue, excluding the carboxyl groups, of an interple, straight and branch chain aliphatic, alkoxy and halnal anhydride of a saturated or unsaturated acyclic aliogen substituted benzenes, aromatic substituted benzene and aromatic ethers, such as, for example propenyl benzene. propylbenzene, butylbenzene, ethyltoluene. butyltoluene, propyltoluene, diphenyl oxide, biphenyl, 0-, mand p-diethylbenzene, dodecylbenzene, octadecylbenzene, bromobenzene; l-bromo-3 chlorobenzene, l-bromo-4-fluorobenzene, l-bromo-2- iodobenzene. l-bromo-3-iodobenzene, l-chloro-4- fluorobenzene, o-dibromobenzene, mdibromobenzene. o-dichlorobenzene, mdichlorobenzene, l,3-dipropoxybenzene. l-ethyl 4- propylbenzene, l-fluoro-4-iodobenzene. 4-bromo-oxylene, oz-bromo-m-xylene, 4-bromo-m-xylene, a-chloro-m-xylene, 4-ethyl-m-xylene, S-ethyl-m-xylene, 2- bromo-p-xylene, a-chloro-pxylene, Z-ethyl-p-xylene, 2-ethyl-p-xylene, o-bromo-toluene, m-bromotoluene. 0-, m-. and p-chlorotoluene, tertiary butylstyrene. a-bromostyrene, B-bromostyrene, a-chlorostyrene, B-chlorostyrene, mixtures thereof and the like.  
  The above compounds may be represented by the following general fromula provided it is understood that such compounds represented by the formula are liquids and have boiling points at atmospheric pressure above about l50C.  
  wherein R R and R are independently selected from an alkyl group having from about 1 to about 18 carbon atoms, an alkenyl group having from 2 to about 3 carbon atoms, a halogen, an alkoxy group, an aromatic group and hydrogen.  
  Other suitable aromatic compounds which may be employed as the liquid modifier compound (Component C) in the present invention include liquid multiring compounds having a boiling point about 150C such as, for example, l-chloronaphthalene, l-bromonaphthalene, mixtures thereof and the like.  
  Suitable partially hydrogenated multi-ring aromatic compounds which may be employed as the liquid modifier compound (Component C) in the present invention include, for example, 1,4-dihydronaphthalene, l,-  
 2,3,4-tetrahydronaphthalene, mixtures thereof and the like.  
  Suitable fatty acids and naturally occurring fatty oils which may be employed as the liquid modifier compounds (Component C) in the present invention includes, for example, oleic acid, linoleic acid, linolenic acid, and the like. The fatty acids resulting from the hydrolysis of naturally occurring oils of animal and vegetable origin including for example, linseed oil, castor oil. tung oil. fish oil, soya oil and the like and such acid as are produced as byproducts in chemical processes including for example, tall oil, the byproduct resulting from the conversion of wood pulp to paper by the sulfate process, mixtures of any of the above and the like.  
  Also operable as the liquid modifier compound are the naturally occurring fatty oils having boiling points above about 150C including, for example, linseed oil, castor oil, tung oil, fish oi], soya oil, and the like.  
  Suitable organophosphorus compounds which may be employed as the liquid modifier compound, Component C, include, for example, organo phosphates, organo phosphites and organo phosphonates having boiling points above about 150C.  
  Organo phosphates, phosphites and phosphonates which may be employed as the liquid modifier compound include those liquid compounds represented by the formulae wherein R R and R are independently selected from the group consisting of alkyl, alkoxyaryl, aryloxyaryl, alkaryl, aralkyl groups and halogen substituted derivatives thereof. Y is oxygen or sulfur, X is a halogen, i.e. chlorine, fluorine, bromine or iodine, n has a value of l to 2. Suitable such compounds include, for example, tri-n-butyl phosphate, triethylphosphate, tricresylphosphate, tris-(beta-chloroethyl)phosphate, His-(2,3- dibromopropyl)phosphate, butyl dichlorophosphate, 2-chloroethyl dichlorophosphate, ethyl dichlorophosphate, diethyl fluorophosphate, bis(2-chloroethyl) fluorophosphate, dibutyl chlorophosphate isoamyl dichlorothionophosphate, ethyl dibromothiophosphate, Z-chlorophenyl dichlorophosphate, Z-methoxyphenyl dichlorophosphate, Z-phenoxyphenyl dichlorophosphate, 2-chloroethyl dichlorophosphite, tris(2-chloroethyl)phosphite, tributyl phosphite, tricresyl phosphite, triethyl phosphite, diethyl isoamylphosphonate, diethyl ethylphosphonate, dimethyl methylphosphonate, di-  
 ethyl methylphosphonate, diisobutyl isobutylphosphonate, bis(2-bromopropyl)-2-bromopropane phosphonate.  
  When haloor dihalo-phosphates or phosphites or their thiono derivatives are employed as the liquid modifier compound (component C), they are preferably added to the composition just prior to the nonamine-containing catalyst so as to minimize their reaction with the hydroxyl groups of the polyol, component A.  
  The organo phosphorus compounds may be prepared by procedures described in ORGANO-PHOSPHORUS COMPOUNDS, G. M. Kosolapoff, John Wiley &amp; Sons, Inc., 1950.  
  Suitable liquid organic carbonates which may be employed as the liquid modifier, component C, in the present invention include the acyclic and cyclic carbonates represented by the formulae wherein each R, and Rare independently aryl, alkyl (having from about I to about 6 carbon atoms) or alkenyl groups (having from about 1 to about 6 carbon atoms) and substituted derivatives thereof and each R and R, are selected from the same groups as R and R and hydrogen.  
  Suitable liquid acyclic organic carbonates which may be employed in the present invention include, for example, bis( 2-chloroethyl)carbonate, di-n-butyl carbonate, butyldiglycol carbonate. cresyldiglycol carbonate, dibutyl carbonate. di-Z-ethylhexyl carbonate, dimethallyl carbonate, dinonyl carbonate and the like. The organic acyclic carbonate may be prepared by procedures given in US. Pat. No. 2,687,425.  
  Suitable liquid cyclic organic carbonates include, for example, propylene carbonate. butylene carbonate, styrene carbonate, mixtures thereof and the like. The cyclic organic carbonates may be prepared in the manner described in Canadian Pat. No. 556,006.  
  Suitable cyclic polyethers which may be employed as the liquid modifier (component C) include, for example, the cyclic tetramer of ethylene oxide, cyclic pentamer of propylene oxide, cyclic tetramer of propylene oxide, mixtures of the above and mixtures of cyclic pentamers and above of ethylene oxide and or propylene oxide. Any liquid cyclic polyether haivng a boiling point above 150C may be employed as the liquid modifier in the present invention including cyclic polyethers prepared from butylene oxide, epichlorohydrin and the like.  
 The liquid cyclic polyether modifier compounds may be prepared by procedures mentioned in Cyclic Polyethers and Their Complexes with metal Salts by C. J.-  
 Pedersen, J. Am. Chem. Soc., Vol. 89, p. 7017-7036, 1968, Twelve-Membered Polyether Rings. The Cyclic Tetramers of Some Olefin Oxides by R. s. Kern; J. Org. Chem., Vol. 33, p. 388-390, 1968; British Pat. Nos. 785,229 and 1,108,921.  
  Suitable halogenated aliphatic compounds having a boiling point above about 150C which may be employed as the modifier compound in the present invention include, for example, tetrabromoethane, bromoform, hexachlorobutadiene, tetrachlorobutadiene, L2 ,3 ,3-tetrachlorobutane, l,5-dibromo-pentane, l ,Z-tribromopropane, 1,2,3-trichloropropene, polyepichlorohydrin diol having an equivalent weight above about 700 up to about 4,000, chlorinated paraffins, e.g. Chlorowax&#34; No. 40, l-mercapto-3- chloropropanol-Z, 3-chloropropanel ,2-diol, 2-chloropropane l,3-diol, l,3-dichloro-2-propanol, mixtures thereof and the like.  
  The halogenated aliphatic compounds which do not contain hydroxyl groups may be employed in quantities of from about 0.2 to about 50 percent by weight of the sum of the weights of components A, B and C, and preferably from about 1 to about percent by weight on the same basis i.e., the sum of the weights of components A, B and C. When the halogenated aliphatic compounds employed herein also contain hydroxyl groups and have a hydroxyl equivalent weight of less than 500, the quantity which is to be employed is from about 0.2 to about 10 and preferably from about 0.4 to about 5 percent by weight based upon the combined weights of A, Band C.  
  Suitable cyclic sulfones which may be employed as the liquid modifier compound include the S-membered cyclic sulfones such as, for example, 3-methylsulfolane (3-methyltetrahydrothiophene-l,l-dioxide) and the like.  
  The term liquid modifier boiling above about 150C&#34; includes eutectic mixtures of the previously described classes of compounds which are solids at atmospheric pressure but said eutectic mixtures are a liquid at room temperature and atmospheric pressure which have boiling points above about 150C. Also included in the definition are those solid compounds of the classes previously described which are dissolved in a liquid member of any of the described classes of compounds having boiling points above about C wherein the resultant solution is a liquid at standard conditions of temperature and pressure and having boiling points at atmospheric pressure above about 150C.  
  Suitable non-amine-containing catalysts for urethane formation include, for example, organo-metal compounds of tin, zinc, lead, mercury, cadmium, bismuth, cobalt, manganese, antimony, iron and the like such as, for example, metal salts of a carboxylic acid having from about 2 to about 20 carbon atoms including, for example, stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, ferric acetylacetonate, lead octoate, lead oleate, phenylmercuric propionate cobalt naphthenate, lead naphthenate, mixtures thereof and the like.  
  It is preferred that the catalysts be employed in liquid form. Those catalysts which are not ordinarily liquids may be added as a solution in a solvent which is compatible with the other components employed in the composition of the present invention. Suitable such solvents include, for example, dioctylphthalate, polyoxyalkylene glycols, mineral spirits, dipropylene glycol, mixtures thereof and the like.  
  It has previously been stated that the quantity of the non-amine-containing catalyst is in the range of from about 0.2 to about 10%. However, when the liquid modifier compound is a non-ester-containing aromatic compound or a halogenated aliphatic compound as described herein, the operable range for the quantity of the catalyst to be employed is from about 0.01 to about 10% and preferably from about 0.05 to about 2% and most preferably from about 0.1 to about 0.5% by weight based upon the combined weights of Components A, B and C.  
  Suitable polyisocyanates which may be employed as Component B in the compositions of the present invention include, for example, any organic polyisocyanate having 2 or more NCO groups per molecule and no other substituents capable of reacting with the hydroxyl groups of the polyoxyalkylene compound. Suitable such polyisocyanates include, for example, 2,4- toluenediisocyanate, 2,6-toluenediisocyanate, hexamethylene diisocyanate, p,p diphenylmethanediisocyanate, p-  
 phenylenediisocyanate, hydrogenated methylene diphenyldiisocyanate (e.g. Hylene W) naphthalene diisocyanate, dianisidine diisocyanate, polymethylene polyphenyl-isocyanate, mixtures of one or more polyisocyanates and the like.  
  Other organic isocyanates which may suitably be employed and which are to be included in the term organic polyisocyanate include isocyanate terminated prepolymers prepared from the previously mentioned polyols and the above mentioned isocyanates.  
  The cured compositions of the present invention vary from transparent solids to white or off-white opaque solids, depending upon the particular liquid modifier compound (component C) and/or polyisocyanate (component B) employed to produce such compositions.  
  Suitable modifier compounds which may be employed to produce solid opaque products include, for example,  
 I. those compounds represented by formula I wherein at least 20% by weight of the compound is derived from units wherein R R R, are hydrogen.  
 2. those compounds represented by formula ll wherein the molecular weight is at least about 1,500;  
 3. those compounds represented by formula III wherein the molecular weight is at least about 3,000; and  
 4. those compounds represented by formula IV wherein the molecular weight is at least about 7,000 and at least of the molecular weight is derived from units wherein R R R, are hydrogen.  
  Suitable modifier compounds which may be employed to produce transparent solid products include. for example,  
 1. those compounds represented by formula I wherein less than about 20% by weight of the compound is derived from units wherein R R R, are hydrogen;  
 2. those compounds represented by formula II wherein the molecular weight is greater than about 700 but less than about 1,500 and wherein less than 207 of the molecular weight is derived from units wherein R,, R R,, are hydrogen;  
 3. those compounds represented by formula III wherein the molecular weight is greater than about 700 and less than about 3,000 and wherein less than about 20% of the molecular weight is derived from units wherein R R R are hydrogen; and  
 4. those compounds represented by formula IV having a molecular weight from about 1,500 to less than about 7,000 and wherein less than about 20% of the molecular weight is derived from units wherein R,, R R,, are hydrogen.  
  Rigid polyurethane products can be prepared by rapidly mixing the components of the compositions of the present invention. It is preferred to thoroughly blend together the components represented by A, the polyol, B, the polyisocyanate and C, the liquid modifier compound and then mixing the resultant mixture with Component D, the catalyst. Mechanical dispensing or combination mixing-dispensing devices can be employed by utilizing 2 or more streams of the individual components or mixtures of the components which are introduced into said device.  
  Other components including inert fillers such as, for example, sand, microballoons. glass fibers, asbestos, aluminum granules. silicon carbide powder and the like, coloring agents, such as pigments and dyes including, for example, chromic oxide, ferric oxide, mixtures thereof and the like may be employed in the compositions of the present invention without detracting from the scope thereof.  
  The compositions of the present invention rapidly produce solid products which may be demolded, i.e. the articles produced therefrom may be removed from the mold, within about 5 minutes, usually within about 3 minutes and preferably within about 1 minute or less from the time the catalyst is blended into the mixture and do nt require the application of external sources of heat to accomplish this, although in some circumstances it may be desirable to post cure, at elevated temperatures, the products in order to develop certain properties. The compositions of the present invention not only can be demolded within 5 minutes and often in less than 2 to 3 minutes, but the cast objects produced therefrom have developed sufficient strength properties to be employed immediately upon cooling to room temperature for their intended purpose. The cast objects are hot or warm to the touch immediately after removing from the mold due to the exotherm generated during the reaction. This is a valuable contribution to the urethane molding art, in that productivity can be increased employing a given quantity of molds.  
  The choice of the catalyst involves the desired time delay between the catalyst being mixed into the reagents and the liquid mix instantly solidifying. For example. if tolylene diisocyanate is used along with a polyol that is the reaction product of glycerine with propylene oxide and having a molecular weight of about 260 plus a polyoxypropylene glycol having a molecular weight of about 4000 as the liquid modifier compound, then the addition of about 1% stannous octoate catalyst will yield a delay or induction time of about 10 seconds before the mixture suddenly *freezes into a solid. Substitution of dibutyltin dilaurate at the same catalyst level stretches this delay time to about 20 seconds, and phenyl mercuric propionate exhibits a delay time of about 120 seconds before extremely rapid solidification occurs.  
  The change of isocyanate to a less reactive one, i.e. the substitution of hexamethylene diisocyanate for tolylene diisocyanate, correspondingly increases the delay time before rapid solidification takes place.  
  Suitable materials from which adequate molds, for casting the compositions of the present invention, may be prepared include polymers such as, for example, polyethylene, polypropylene. their copolymers and the like. polurethanes, polysiloxane elastomers, Mylar. cured polyepoxides. mixtures thereof and the like.  
  It is preferred to employ relatively thin wall molds 0r molds having a low heat capacity or thermal conductivity. Heavy molds made of relatively high thermal conductivity mateirals such as aluminum. copper, iron or steel and the like may present curing problems, i.e. the reactants may not be readily demolded unless the mold is preheated at about 50-90C. especially when casting relatively thin sections. However. high thermal conductivity materials such as copper or aluminum can be employed as thin wall molds without preheating if the thermal capacity of the mold is relatively low compared to the amount of heat liberated in the casting.  
  The compositions of the present invention are useful as, but not restricted to such uses as. a casting material for preparing bearing surfaces. annular spacers. decorative objects. furniture or furniture components, gears or other machine components, threaded protective plugs and caps, and the like.  
  The following examples are illustrative of the present invention but are not to be construed as to limiting the scope thereof in any manner.  
  The following examples l-l0 are illustrative of solid, rigid, opaque and translucent products.  
 EXAMPLE 1 A. An Example of the Present Invention In a suitable container were thoroughly blended 30 grams of Voranol CP-260 (the reaction product of glycerine with propylene oxide having a molecular weight of about 260) as the polyol, 30 grams of P-4000, a polyoxypropylene glycol having a molecular weight of about 4.000, as the liquid modifier compound and 30 grams of Hylene TM (an /20 mixture by weight of the 2.4-and 2,6-isomers of tolylene diisocyanate having an NCO equivalent weight of about 87).  
  After the above components were well mixed, 1 cc of a liquid dibutyltin dilaurate, commerically available as T-l2 catalyst from Metal and Thermit Corp., was rapidly stirred in and the resultant mixture was poured into a polyethylene beaker. Thirty seconds after stirring in the catalyst, the mixture suddenly turned an opaque white color and underwent substantially instantaneous hardening. Sixty seconds after the catalyst was added, a rigid, hard, white, opaque polymer casting was demolded, i.e. removed from the polyethylene beaker, and was found to have a density of l.055 grams/cc.  
 B. Comparative Demonstration Effect of One-Tenth the Amount of Catalyst The same procedure and composition as in A above was employed except that 0.1 cc of the dibutyltin dilaurate catalyst was employed with the following results.  
  60 seconds after the catalyst was added, the mixture was still a transparent liquid.  
  120 seconds after the catalyst was added, the mixture was an opaque liquid.  
  180 seconds after the catalyst was added, the mixture hardened but was too tacky to be demolded.  
  400 seconds after the catalyst was added, the casting was demolded.  
  The product was found to be a warped, rigid, white, opaque solid that was filled with gross bubbles or gas cells. This casting had a density of 0.864 grams/cc.  
 C. Comparative Demonstration of Effect of Omitting the Liquid Modifier Same procedure as in A above employing 33 grams of the indicated polyol and 33 grams of the polyisocyanate. The mixture suddenly gelled after the catalyst addition; however within the next 4 minute interval, the cast polymer grossly swelled and generated copious quantities of internal gas bubbles and open fissures across the top surface of the casting. The cured polymer mass had a density of 0.56 grams/cc. EXAMPLES EMPLOYING VARIOUS POLYISCYANATES:  
 EXAMPLE 2 Same procedure as in Example 1A employing the fol lowing components:  
 33 grams of Voranol CP-260 as the polyol 33 grams of P4000 as the liquid modifier 50 grams of Isonate 143L (dimerized diphenylmethanediisocyanate having an NCO equivalent weight of about 144 and a functionality of about 2.25)  
 1 cc lead octoate containing 24% Pb.  
  In less than 15 seconds after catalyst addition, the mixture suddenly solidified into a cream-colored, opaque, hard, rigid polymer which was demoldable within 40 seconds.  
 EXAMPLE 3 Same procedure as in Example lA employing the following components:  
 30 grams of Voranol CP-260 30 grams of P-3000 (a polyoxypropylene glycol having an average molecular weight of about 3,000) as the liquid modifier 45 grams of Hylene W (hydrogenated methylene diphenyldiisocyanate having an NCO equivalent 12 weight of about 132 and a functionality of about 2). I cc of lead octoate having 24% Pb. The mixture suddenly turned into an opaque, dense, hard solid within about seconds and could be demolded within about 40 seconds.  
 EXAMPLE 4 Same procedure as in Example 1A employing the following components.  
  grams of Voranol CP-260 30 grams of P-3000 32 grams of Takenate 500 (Xylylene diisocyanate having an NCO equivalent weight of about 94 and an average functionality of about 2). 1 cc of lead octoate (24% Pb). The mixture suddenly turned into an opaque, white solid within about 30 seconds and could be demolded within about 50 seconds.  
 EXAMLES EMPLOYING VARIOUS POLYOLS EXAMPLE 5 Same procedure as in Example IA employing the following components.  
 26 grams of Voranol CP450 (reaction product of glycerine with propylene oxide having a molecular weight of about 450).  
 15 grams of P-4000 16 grams of Hylene TM 1 cc of lead octoate (24% Pb) The mixture rapidly set to produce a rigid, hard,  
 opaque, white, solid, casting within about 25 seconds which could be demolded within about 40 seconds.  
 EXAMPLE 6 Same procedure as in Example IA employing the following components.  
  30 grams of the reaction product of glycerine with ethylene oxide in a molar ratio of 1:3 and having a hydroxyl equivalent weight of about 75.9. 30 grams P-4000 30 grams Hylene TM I cc lead octoate (24% Pb) The mixture suddenly set into a hard, rigid, white, opaque solid product within about 30 seconds which could be demolded within about seconds.  
 COMPARATIVE EXAMPLE 6A EXAMPLES OF VARIOUS LIQUID POLYOXYALKYLENE MODIFIER COMPOUNDS: EXAMPLE 7 EXAMPLE 8 Same procedure as in Example lA employing the following composition.  
 33 grams of Voranol CP-260 33 grams of the adduct of propylene oxide onto butanol and having a molecular weight of about 2.000.  
 33 grams of Hylene TM 1 cc of lead octoate (24% Pb).  
  The mixture set into a rigid, white, opaque. solid product within about 20 seconds which could be demolded within about 40 seconds.  
 EXAMPLE 9 Same procedure as in Example 1A employing the following composition.  
 30 grams of Voranol CP-260 32 grams of the adduct of 80-20 mole percent mixture of propylene oxide and ethylene oxide onto a glycerine-propylene oxide adduct haivng a molecular weight of about 260, the molecular weight of the resultant product being about 10,000. 30 grams of Hylene TM 1 cc of lead octoate (24% Pb) The mixture rapidly set into an opaque. white, hard, solid product within about 20 seconds and could be demolded within about 40 seconds.  
 EXAMPLE Same procedure as in Example lA employing the following composition.  
 30 grams of Voranol CP-260 30 grams of propylene glycol initiated polyepichlorohydrin having an average molecular weight of about 2,000.  
 30 grams Hylene TM 1 cc of lead octoate (24% Pb) The composition rapidly set into a hard, opaque, rigid, solid product within about seconds which was readily demoldable within about 40 seconds.  
  The following examples 1 1-19 are illustrative of solid, rigid, transparent products.  
 EXAMPLE ll Same procedure as in Example IA employing the following composition.  
  grams of Voranol CP-260 30 grams of Voranol CP-470l (the reaction product of glycerine with propylene oxide end-capped with ethylene oxide and having an averagemolecular weight of about 4,700) 30 grams of Hylene TM 1 cc lead octoate The mixture instantly set into a rigid. transparent, solid product within about 20 seconds and could be demolded within about 30 seconds. The casting had a density of 1.1 grams/cc.  
 EXAMPLES OF VARIOUS POLYISOCYANATES. POLYOLS AND MODIFIER COMPOUNDS EXAMPLE 12 Same procedure as in Example lA employing the following composition.  
 33 grams of Voranol CP-260 33 grams of Voranol CP-3000 (glycerine initiated polyoxypropylene glycol having an average molecular weight of about 3.000) 50 grams lsonate 143L 1 cc T-9 catalyst (stannous octoate commerically available from Metal and Thermit Corp.). The mixture rapidly set into a rigid. transparent. solid within about 15 seconds and could be demolded within about 30 seconds.  
 EXAMPLE 13 Same procedure as in Example 1A employing the following composition.  
 30 grams of Voranol CP-260 30 grams of Voranol CP-l500 (glycerine initiated polyoxypropylene glycol having an average molecular weight of about 1,500) 30 grams of Hylene TM 1 cc of T-9 catalyst The mixture instantly set into a transparent. solid product within about 40 seconds and could be demolded within abput 60 seconds.  
 COMPARATIVE EXAMPLE l3-A Same procedure as in Example lA employing the following composition.  
 30 grams of voranol C P-260 30 grams of Voranol CP-700 (glycerine initiated polyoxypropyleneglycol having an average molecular weight of about 700) 30 grams of Hylene TM 1 cc T-9 catalyst The mixture demonstrated instant set characteristics but the product swelled and cracked.  
 EXAMPLE 14 Same procedure as in Example lA employing the following composition.  
  30 grams of Voranol CP-260 31 grams of a trio] prepared by reacting glycerine with a mixture of propylene oxide and ethylene oxide having an average molecular weight of about 4,100 and about 16 weight percent ethylene oxide). 30 grams Hylene TM 1 cc lead octoate (24% lead) The mixture instantly set within about 30 seconds and the rigid, solid, clear casting was demolded within about 50 seconds. i  
 EXAMPLE 15 Same procedure as in Example 1A employing the following composition.  
 30 grams of the reaction product of glycerine with propylene oxide in a molar ratio of about 1:3 respectively.  
 30 grams Voranol CP-4701 (glycerine initiated polyoxypropylene glycol end-capped with ethylene oxide) 45 grams Hylene W 1 cc lead octoate (24% Pb) At the end of 180 seconds the mixture was still liquid; at 195 seconds the mixture began to gel rapidly, and at 210 seconds the casting was a rigid transparent tackfree solid.  
  When the same formulation was catalyzed by 5 cc of 24% Pb octoate. the solidification was not greatly accelerated, e.g. the mix was still liquid at 120 seconds, gelling occurred rapidly at 135 seconds, and the product was a transparent rigid solid at 150 seconds after catalyst addition.  
 EXAMPLE 16 EXAMPLE 17 Same procedure as in Example 1A employing the following composition.  
 26 grams of Voranol CP-450 (glycerine initiated polyoxypropylene glycol having an average molecular weight of about 450).  
  grams of Voranol CP-4701 16 grams of xylylene diisocyanate 0.7 cc of lead octoate (24% Pb) The mixture instantly set into a transparent, rigid,  
 solid product within about 30 seconds which could be demolded within about 50 seconds.  
 EXAMPLE 18 Same procedure as in Example 1A employing the following composition.  
 33 grams of Voranol CP-260 33 grams ofa butanol initiated polyoxypropylene glycol having an average molecular weight of about 1000. 33 grams of Hylene TM 1 cc of lead octoate catalyst The mixture instantly set into a transparent, rigid, dense product within about seconds and could be demolded within about 35 seconds.  
 EXAMPLE 19 Same procedure as in EXAMPLE 1A employing the following composition.  
 35 grams of Voranol CP-260 30 grams of a polyoxypropylene glycol having an average molecular weight of about 1,000. 35 grams of Hylene TM 1 cc of lead octoate (24% Pb) 5 The mixture instantly set into a transparent, rigid,  
 dense product within about 10 seecond and could be demolded within about 30 seconds.  
 EXAMPLE 20 EXAMPLE 21 33 grams of Voranol CP-260 30 grams of distilled Tall oil 45 grams of PAP] (polymethylenepolyphenylisocyanate having an average functionality of about 2.6 and and NCO equivalent weight of about 133) 1 cc T-9 catalyst About 35 seconds after catalyst addition, the mixture suddenly froze into a rigid, solid material having a density of 1.04 grams/cc.  
 EXAMPLE 22 Same procedure as in Example 1A employing the following components:  
 30 grams of the reaction product of pentaerythritol with propylene oxide in a molar ratio of 1 to 5 respectively.  
 30 grams of linseed oil 30 grams of toluene diisocyanate 1 cc of T-9 catalyst The mixture suddenly set into a dense, solid product.  
 EXAMPLE 23 EXAMPLE 24 Same procedure as in Example 1A employing the following components:  
 30 grams of Voranol CP-260 20 grams of oleic acid 46 grams of PAP] (polymethylene polyphenylisocyanate) 1 cc of T-9 catalyst About seconds after catalyst addition, the mixture suddenly set into a rigid, light brown casting which had a density of about 1.04 grams/cc.  
 EXAMPLE 25 Same procedure as in Example 1A employing the following components:  
 30 grams of the reaction product of glycerine with propylene oxide to a molecular weight of about 260.  
 20 grams of linseed oil 46 grams of PAP] 1 cc of T-9 catalyst The mixture suddenly set into a rigid. khaki-colored.  
 opaque, solid within about seconds after catalyst ad dition. The casting was demolded within about 1 minute after catalyst addition and had a density of 1.12 grams/cc.  
 EXAMPLE 26 Same procedure as in Example lA employing the following components:  
  grams of the reaction product of glycerine with propylene oxide to a molecular weight of about 260.  
 20 grams of castor oil 46 grams of PAPI 1 cc of T-9 catalyst About 25 seconds after catalyst addition. the mixture set into a rigid, solid which was demolded in about 1 minute after catalyst addition. The casting had a density of 1.12 grams/cc.  
 EXAMPLE 27 Same procedure as in Example 1A employing the following components:  
 30 grams of Voranol CP-26O 30 grams of Hylene TM 30 grams of l.2,3.4-tetrahydronaphthalene l cc of lead octoate (24% Pb) About l5 seconds aftercatalyst addition. the mixture suddenly set into a rigid. clear. transparent. solid.  
 EXAMPLE 28 seconds later. The product had the following proper- UCSI Density l gram/cc Shore D Hardness about 92 EXAMPLE 29 Same procedure as in Example 1A employing the following components:  
 30 grams reaction product of glycerine with propylene oxide to a molecular weight of about 260. 30 grams of 1,2,4-trichlorobenzene 30 grams toluenediisocyanate LII  1 cc lead octoate About 15 seconds after catalyst addition. the mixture suddenly set into a rigid. transparent solid.  
 EXAMPLE 30 Same procedure as in Example lA employing the following components:  
 35 grams of the reaction product of glycerine with propylene oxide to a molecular weight of about 260.  
 20 grams of l,2.3,4-tetrahydronaphthalene 10 grams of 1,2.4-trichlorobenzene 35 grams of toluene diisocyanate 0.3 cc of lead octoate The mixture suddenly set into a rigid, transparent solid.  
 EXAMPLE 31 Same procedure as in Example 1A employing the following components:  
 30 grams of the reaction product of glycerine with propylene oxide to a molecular weight of about 260.  
 30 grams of a-chloronaphthalene 30 grams of toluenediisocyanate 0.4 cc of lead octoate About 20 seconds after catalyst addition. the mixture suddenly set into a rigid. transparent solid.  
 EXAMPLE 32 A. Same procedure as in Example lA employing the following components 30 grams of the reaction product of glycerine with propylene oxide to a molecular weight of about 260.  
 30 grams of 1.2.4-triethylbenzene (b.p. approx.  
 30 grams of toluenediisocyanate 0.4 cc of lead octoate About 30 seconds after catalyst addition, the mixture suddenly set into a rigid, opaque solid. About 45 seconds after catalyst addition. the casting was demolded and had a density of 1.12 grams/cc.  
 B. Comparative Example Use of Modifier Compound With a Boiling Point Below About C Same procedure as in Example 1A employing the following components:  
 30 grams of the reaction product of glycerine with propylene oxide to a molecular weight of about 260.  
 30 grams of ethylbenzene (b.p. approx. 136C) 30 grams of toluene diisocyanate 0.4 cc of lead octoate About 20 seconds after catalyst addition, the mixture suddenly swelled with gross bubble formation to yield an expanded rigid casting having an apparent density of 0.67 grams/cc.  
 EXAMPLE 33 Same procedure as in Example l-A employing the following composition:  
 30 grams of the reaction product of glycerine with about 3 moles of ethylene oxide per mole of glycer- 32 grams xylylene diisocyanate 30 grams tris( 2-chloroethyl)phosphate 0.5 cc lead octoate The mixture instantaneously set within about 15 seconds after catalyst addition and was demolded within about 30 seconds after catalyst addition thereby producing a clear, transparent. rigid, non-brittle solid casting having a density of about 1.25 grams/cc.  
 EXAMPLE 34 Same procedure as in Example l-A employing the following composition:  
 30 grams of the reaction product of glycerine with 3 moles of propylene oxide per mole of glycerine having a hydroxyl equivalent weight of about 87.  
 46 grams PAPl (polymethylene polyphenylisocyanate) 20 grams tri-n-butylphosphate 1 cc stannous octoate catalyst The mixture suddenly solidified within about 20 seconds after catalyst addition and the resultant casting was demolded within about 30 seconds after catalyst addition. The product was a tough, dark colored (transparent in very thin sections) solid, rigid product having a density of 1.15 grams/cc.  
 EXAMPLE 35 Same procedure as in Example 1A employing the following composition.  
 30 grams Voranol CP-26O 30 grams toluenediisocyanate 30 grams tricresyl phosphate cc lead octoate (24% lead) The mixture was cast as a sheet and within about seconds after catalyst addition, suddenly solidified into a tough, colorless, transparent rigid solid.  
 EXAMPLE 36 Same procedure as in Example 1A employing the following composition:  
 30 grams of the reaction product of glycerine with propylene oxide in a molar ratio of about 1:3 having a hydroxyl equivalent weight of 87. 30 grams of toluene diisocyanate 30 grams of triethylphosphate 0.5 cc. of lead octoate The mixture was cast as a sheet which instantly set into a transparent. relatively soft sheet having an elongation less than about 100 percent. The relative softness of this product is believed to have been derived from a side effect of the triethylphosphate also functioning as a plasticizer at this concentration.  
 EXAMPLE 37 Same procedure as in Example 1A employing the following composition.  
 30 grams of Voranol CP-26O 30 grams of toluene diisocyanate 30 grams of tributylphosphite 0.5 cc of lead octoate The mixture suddenly solidified into an opaque, white, rigid casting within about 10 seconds after catalyst addition.  
 &#39; EXAMPLE 38 Same procedure as in Example lA employing the following composition.  
 30 grams of Voranol CP-26O 30 grams of toluene diisocyanate grams of bis(2-bromopropyl)2-bromopropane phosphonate 1 cc of stannous octoate (T-9) The mixture suddenly solidified into a transparent, solid, rigid casting within about 20 seconds after catalyst addition and was demolded. within about 40 seconds after catalyst addition.  
 EXAMPLE 39 Same procedure as in Example 1A employing the following composition.  
  grams of Voranol CP-260 30 grams of tris( 2-chloroethyl)phosphate 75 grams of ISONATE 143L (a diphenylmethane diisocyanate which has been dimerized with phosphoric acid and having an NCO equivalent weight of about 144 and an average functionality of about 2.25) lcc of dibutyl tin dilaurate The above mixture was cast onto a Mylar sheet and suddenly solidified within about 20 seconds after catalyst addition and within about 40 seconds after catalyst addition a rigid, yellow-brown, transparent sheet was removed from the casting surface.  
 Test specimens cut from the above prepared sheet had the following properties.  
  tensile strength (ultimate) 7500 psi 7r elongation l0 Hardness. Shore D EXAMPLE 40 EXAMPLE 41 Same procedure as in Example l-A employing the following composition:  
 30 grams of Voranol CP-260 20 grams of bis(2-chloroethyl)carbonate 20 grams of toluene diisocyanate 0.5 cc of stannous octoate The mixture suddenly solidified within about 10 seconds after catalyst addition which was demolded within about 20 seconds after catalyst addition thereby producing a transparent, rigid dense casting.  
 EXAMPLE 42 Same procedure as in Example l-A employing the following composition:  
 45 grams of Voranol CP-260 30 grams of propylene carbonate 69 grams of polymethylene polyphenylisocyanate 1 cc of stannous octoate The above mixture was cast onto a Mylar sheet which instantly set within about seconds after catalyst addition.  
  The dark brown, rigid, transparent product was removed from the Mylar casting surface within about 45 seconds after catalyst addition. The product was found to possess the following properties.  
 tensile strength 4940 psi elongation 12% Hardness. Shore D 87 EXAMPLE 43&#39; Same procedure as in Example l-A employing the following composition:  
 30 grams of the reaction product of glycerine with ethylene oxide in a molar ratio of 1:3 respectively having a hydroxyl equivalent weight of about 75.9.  
 32 grams of xylylene diisocyanate 30 grams of the cyclic tetramer of ethylene oxide 0.5 cc of lead octoate (24% Pb) The mixture suddenly solidified within about 15 seconds after catalyst addition and the casting was demolded within about 25 seconds after catalyst addition. The casting was a transparent rigid solid which had a density of 1.2 grams/cc.  
 EXAMPLE 44 Same procedure as in Example l-A employing the following composition grams of Voranol CP-260 30 grams of toluene diisocyanate 30 grams of a mixture of cyclic polyethers of propylene oxide containing pentamer and higher homologs.  
 1 cc of lead octoate.  
  The mixture suddenly solidified within about 12 seconds after catalyst addition and the solid product was demolded within about 30 seconds after catalyst addition yielding a translucent, rigid off-white casting having a density of 1.15 grams/cc.  
 EXAMPLE 45 Same procedure as in Example 1A employing the following composition.  
 30 grams of the reaction product of pentaerythritol with propylene oxide in a molar ratio of about 1:5 respectively and having a molecular weight of about 415-430.  
 46 grams of PAPI (polymethylene polyphenylisocyanate) 30 grams of the cyclic tetramer of propylene oxide.  
 1 cc of stannous octoate (T-9).  
  The composition suddenly set within about 25 seconds atter catalyst addition to yield a dark, rigid, casting having a density of 1.09 grams/cc which was readily demolded within seconds after catalyst addition.  
 EXAMPLE 46 Same procedure as in Example l-A employing the following composition:  
 32 grams of Voranol CP-260 32 grams of toluene diisocyanate (80/20 mixture of 2,4- and 2,6-isomers) 3 grams ofChlorowax&#34; No. 40 (a liquid chlorinated paraffin having a specific gravity of 1.15, a viscosity of 25 poises at 25C, manufactured and sold by Diamond-Shamrock Chemicals) 0.5 cc of lead octoate The mass suddenly set, within about 10 seconds after catalyst addition, into a rigid casting having a density of 1.2 grams/cc and had no visual indications of cracks, distortions or bubble formation.  
 EXAMPLE 47 EXAMPLE 48 Same procedure as in Example l-A employing the following composition:  
 30 grams of Voranol (P-260 30 grams of toluene diisocyanate )/20 mixture of 2,4- and2,6-isomers) 0.5 cc of lead octoate (24% lead) 20 grams tetrabromoethane The blend suddenly solidifed within about 15 seconds after catalyst addition and was demolded within about 30 seconds after catalyst addition thereby producing a dense, rigid, bubblefree casting having a density of 1.58 grams/cc.  
 EXAMPLE 49 Same procedure as in Example l-A employing the following composition.  
 37 grams of Voranol CP-260 37 grams of toluene diisocyanate (80/20 blend of 2,4 and 2,6-isomers) 3 grams of tetrabromoethane 0.5 cc of lead octoate (24% lead) The mixture suddenly set within about 15 seconds after catalyst addition to yield a dense rigid, bubblefree casting.  
 EXAMPLE 50 Same procedure as in Example l-A employing the following composition.  
 30 grams of Voranol CP-26O 30 grams of TDI (80/20 mixture of 2,4- and 2,6-  
 isomers) 25 grams of 1,10-dibromodecane 0.5 cc of lead octoate The mixture suddenly solidified within about 15 seconds after catalyst addition and was demolded within about 30 seconds after catalyst addition to provide a dense. rigid, bubbleand crack-free casting having a density of 1.35 grams/cc.  
 EXAMPLE 51 Same procedure as in Example l-A employing the following composition.  
 30 grams of Voranol CP-260 30 grams of toluene diisocyanate (80/20 mixture of 2.4- and 2.6-isomers) 30 grams of bromoform 0.5 cc of lead octoate The mixture solidified within about 15 seconds providing a dense, rigid. bubble-free casting.  
 EXAMPLE Same procedure as in Example l-A employing the following composition.  
 30 grams of Voranol CP-260 30 grams of hexachlorobutadiene 30 grams of toluene diisocyanate (80/20 mixture of 2,4- and 2.6-isomers) 1 cc of lead octoate The mixture solidified to within seconds after catalyst addition to provide a dense, rigid, bubble-free casting.  
 EXAMPLE 53 Same procedure as in Example l-A employing the following composition.  
 32 grams of Voranol CP-260 32 grams of toluenediisocyanate (80/20 mixture of 2,4- and 2.6-isomers) 4 grams of polyepichlorohydrin diol* having a molecular weight of about 2000 The polyepichlorohydrin diol was prepared by slowly adding over a period of about 1 hour 17 pounds of epichlorohydrin to a mixture containing 15 pounds of benzene. 400 grams of 48% aqueous fluoroboric acid and 503 grams of water. The epichlorohydrin addition was conducted at 47C and digested for about 30 minutes at 47C; 40 pounds of benzene was added and 155 pounds of epichlorohydrin was added over a 5% hour period and digested at 47C for about 30 minutes. The water was removed via a water-benzene azeotrope at 90C for 2 hours after neutralizing the catalyst with 5% pounds of 4% aqueous NaOH. The benzene-polvepichlorohydrin mixture was filtered and the henzene removed at )0 C at reduced pressure in about 2 hours. The product contained 1.72% OH by analysis.  
 0.5 cc of lead octoate The mixture rapidly set into a dense, rigid casting having a density of 1.2 grams/cc.  
 EXAMPLE 54 Same procedure as in Example 1A employing the following composition:  
 40 grams of Voranol CP-260 40 grams of toluene diisocyanate (80/20 mixture of 2,4- and 2,6-isomers) 40 grams of Chlorowax No. 40  
 0.5 cc of lead octoate The mixture rapidly solidified thereby forming a dense, rigid casting having a density greater than 1 gram/cc.  
 EXAMPLE 55 (COMPARATIVE) This comparative example illustrates the inoperability of halogenated aliphatic compounds having a boiling point below 150C. Same procedure as in Example l-A employing the following composition:  
 30 grams of Voranol CP-26O 30 grams of perchloroethylene (boiling point 30 grams of toluenediisocyanate (80/20 mixture of 2,4- and 2,6-isomers) 0.8 cc of lead octoate The above mixture suddenly expanded within about 15 seconds after catalyst addition into a non-uniform cellular rigid mass having a density of 0.48 gram/cc.  
 EXAMPLE 56 Same procedure as in Example l-A employing the following composition:  
 30 grams of Voranol CP-260 30 grams of toluene diisocyanate (80/20 mixture of 2,4- and 2,6-isomers) 40 grams of oz-chloronaphthalene 0.05 cc of lead octoate (24% lead) The mixture suddenly solidified about seconds after catalyst addition to yield a transparent rigid polymer which was demolded about 90 seconds after catalyst addition. The density of this casting was found to be 1.17 grams/cc.  
 EXAMPLE 57 Same procedure as in Example l-A employing the following composition:  
 30 grams of Voranol CP-260 30 grams of toluene diisocyanate (80/20 mixture) 15 grams of Voranol CP-1500 15 grams of triethylbenzene 0.05 cc of lead octoate (24% lead) This blend was cast into a polyethylene mold and the blend suddenly solidified about 50 seconds after cata- I lyst addition and was removed from the mold seconds after catalyst addition. This transparent rigid casting was found to have a density of 1.16 grams/cc.  
 EXAMPLE 58 EXAMPLE 59 Same procedure as in Example l-A employing the following composition:  
 60 grams of Voranol RS-350 30 grams of toluene diisocyanate (/20 mixture) 30 grams of trichlorobenzene 1 cc of lead octoate (24% lead) This blend was cast into a polyethylene mold and was found to solidify about 15 seconds after catalyst addition; the casting was removed from the mold 25 seconds after catalyst addition.  
 EXAMPLE 60 Same procedure as in Example l-A employing the following composition:  
  grams of Voranol CP-260 130 grams of toluenediisocyanate (80/20 mixture) 20 grams of chlorowax No. 40&#34;  
 0.5 cc of lead octoate (24% lead) This blend was cast into a Mylar tray and was found to solidify and be removed from the Mylar tray as a dense rigid sheet in less than 60 seconds after catalyst addition. Appropriate tensile bars were cut from this cast resin and were found to exhibit an ultimate tensile of 15,600 psi at elongation.  
 EXAMPLE 61 Same procedure as in Example l-A employing the following composition:  
 30 grams of Voranol (P-260 grams of toluenediisocyanate (80/20 mixture) 25 grams of hydrogenated methylene diphenyl isocyanate (Hylene W) 10 grams of Chlorowax No. 40&#34;  
 1 cc of lead octoate (24% lead) This blend was cast and was found to suddenly solidify seconds after catalyst addition. The rigid casting was demolded 40 seconds after catalyst addition and was found to have a density of 1.10 grams/cc.  
 EXAMPLE 62 Same procedure as in Example l-A employing the following composition:  
 300 grams of the reaction product of glycerine with 3 moles of propylene oxide per mole of glyeerine.  
 400 grams of a prepolymer prepared from the reaction product of 3 moles of propylene oxide per mole of glycerine and toluene diisocyanate. said prepolymer containing 31% NCO.  
 300 grams of trichlorobenzene 1 cc of lead octoate (24% Pb) This liquid blend was cast between 2 parallel sheets of polyethylene; the liquid mix was found to solidify in less than 1 minute after catalyst addition and the cast product was removed from the mold in less than 2 minutes after catalyst addition. This casting was found to be transparent and bubble-free.  
 EXAMPLE 63 Same procedure as in Example l-A employing the following composition:  
 60 grams of Voranol RS-350 30 grams of toluene diisocyanate (80/20 mixture) 20 grams of 3-methylsulfolane 1 cc of lead octoate (24% Pb) This liquid blend solidified in less than 30 seconds and was demolded about 30 seconds later to yield a hard, transparent, rigid casting.  
 EXAMPLE 64 6- and had physical properties as indicated m the table be low.  
 B. Comparative Same procedure as in Example l-A employing the following composition:  
 105 grams of Voranol CP-700 (OH equivalent wt.  
  approx. 232) 5 30 grams of l-lylene TM 40 grams of Voranol CP4701 1 cc of lead octoate (24% Pb) This blend was also cast into a Mylar tray and was found to solidify 35 seconds after catalyst addition. The weak, rubbery transparent cast sheet was removed from the mold about 20 seconds after catalyst addition and had properties as indicated in the table below, which shows that polyols employed as component A having an OH equivalent weight above 230 do not produce the products of the present invention ie the percent elongation was greater than 80%.  
  The following examples demonstrates the use of byproduct streams containing mixtures of aromaticcontaining compounds.  
 EXAMPLE 65 Same procedure as in Example l-A employing the following composition:  
 30 grams of the reaction product of glycerine with propylene oxide in a molar ratio of 1:3 respectively, said product having a molecular weight of about 260.  
 30 grams of a mixed stream of aromatic-containing compounds as the residue stream obtained from the manufacture of ethyl benzene and having a typical composition by weight as follows:  
 3% treithylbenzene 1 1% tetraethylbenzene 1% pentaethylbenzene 3% bis-ethylphenylethane 8% ethylphenyl-phenylethane 13% 1,1-diphenylethane 61% higher boiling components 30 grams of toluenediisocyanate (80/20 mixture of 2,4- and 2,6-isomers) 1 cc of stannous octoate T-9 (M &amp; T Chemicals) The blend was cast into a polyethylene mold and suddenly solidified within 20 seconds after catalyst addition. The rigid, dense casting was demolded within 60 seconds after catalyst addition.  
 EXAMPLE 66 A. Present Invention Same procedure as in Example l-A employing thhe following composition:  
 60 grams of Voranol RS-350 30 grams of toluene diisocyanate 60 grams of Voranol CP-3000 0.5 cc of lead octoate (24% Pb) The mixture was cast as a sheet in a Mylar tray and allowed to cure overnight at room temperature.  
 B. Prior Art Comparison Same procedure as in Example l-A employing the following composition:  
 60 grams of Voranol RS-350 30 grams of toluenediisocyanate 60 grams of dioctylphthalate 0.5 cc of lead octoate (24% Pb) The mixture was cast as a sheet in a Mylar tray and 28 The mixture slowly set within about 60 seconds which could be demolded with difficulty within about 90 seconds. The product was an opaque, rigid solid which had many bubbles and a density of about 0.63  
 allowed to cure overnight at room temperature. grams/cc.  
  C. After curing overnight, each of the panels from A C. Same procedure as in Example lA employing the and B above were sprayed with Krylon black enamel in following composition. 2-inch wide stripes. After 2 hours of drying at room 30 ms f Voran l CP-260 temperature. the paint coating was found to be poorly 30 grams f v l CP 3()00 attached to panel B. an example of the prior art. but 30 grams f Hylen TM was well tacky to panel A. an example of the present 2 c f N,N.N,N-tetramethyl-l,3-butane diamine. invemion- The mixture slowly set within about 120 seconds to D. Another portion of each of panels A and B were produce an ue, tacky, foam-like product which sprayed with 2 inch wide stripes of Illinois Bronzehad a density of 0.51 gram/cc. Powder and Paint Co.s Flat Black No. 607. The paint Th f ll i example d t t the s perior d ied it an hour 11 Plmel the Present invention. solvent resistance of the present invention as compared whereas on Panel B. the prior art. the panel was stil to h d t of US, Pat, No, 3,378,511. tack after 6 hours.  
  After 72 hours of drying at room temperature, a fin- EXAMPLE 68 (COMPARATIVE) germ!&#34; Scratch removed P from Panel B, the Prior Three rigid castings were prepared by the procedure Panel; Whereas Panel] A the Present invention, of Example l-A employing the following formulations. sisted removal of paint by fingernail scratching. A fin- F l i A (P I i g r p r ry g p also removed paint r 30 grams of the reaction product of glycerine with panel B. the prior art, whereas no paint was removed propylene id i a molar ratio f about 13 by this test from panel A. the present invention. spectively Some amine type catalysts will catalyze the urethane rams of toluene diisocyanate reaction to produce instant set products, but the resul- 30 am f vor ol P-4000 tant products are of low density. i.e. less than about l 1 cc f l d cto t (24% Pb) gram/cc and contain many bubbles which adversely af- F l i B (P I i fect the physical properties. This inoperability of the 30 30 grams f th tio duct f glycerine and amine type catalysts insofar as the present invention in propylene ide t a m l r rati f ab t 1:3 reconcerned is demonstrated by the following comparaspectively tive Example 67. 30 grams of toluene diisocyanate 20 grams of trichlorobenzene EXAMPLE 67 (COMPARATlVE) 02 cc of lead octoate A, Same procedure as in Example 1A employing the Formulation C (Prior Art Teachings US. Pat. No. following composition. 3,378,511):  
 30 grams of Voranol CP-260 30 grams of the reaction product of glycerine and 30 grams of Voranol CP-3000 propylene oxide in a molar ratio of about 1:3 re- 30 grams of Hylene TM 40 spectively 1 cc of a 33% solution of diethylenetriamine in di- 30 ms f toluene diis cyanate propyleneglycol. 30 grams of diisodecyl phthalate The mixture slowly set within about 90 seconds to 1 cc of lead octoate (24% Pb) produce an opaque, tacky, rubbery polymer containing Each of the above formulations A, B and C suddenly many bubbles and having a density of 0.6 grams/cc. solidified into a dense, rigid casting within about 30 The casting could be demolded with difficulty within seconds after catalyst addition and were demolded about I20 seconds. within about 60 seconds.  
  B. Same procedure as in Example 1A employing the Several AX %X 1% specimens were cut from the following composition: castings of Formulations A, B, and C and immersed in 30 grams of Voranol CP-260 various solvents at room temperature. Periodic obser- 30 grams of Voranol CP-3000 vations were taken to ascertain the condition of each 30 grams of Hylene TM specimen after exposure to the solvents. The solvents 2 cc of triethylamine and observations are given in the following Table.  
 OBSERVATION SOLVENT Formulation A Formulation B Formulation C Acetone no change after no change severe cracks 1 hr. exposure after l hr. developed after exposure 1 hr. exposure Tetrahydrofuran slight trace not tested severe cracking of cracking and swelling after 1 hr.  
  exposure Methylene chloride slight trace no change severe cracking of cracking after 1 hr. with particles after I hr. exposure separating exposure from specimen after I hr.  
  Continued OBSERVATION SOLVENT Formulation A Formulation B Formulation C Ethylene dichloride intact after no change developed severe 36 hours of after hrs. cracks after exposure of exposure 5 hrs. of exp..  
  total disintegration into discrete particles after 36 hrs. exp. Ethyl Acetate no change no change slight decrcpi after 36 hrs. after 7 hrs. tation into of exposure of exposure discrete particles alter 7 hrs. and total disintegration after 36 hrs.  
  exposure. Methylisohutyl no change after slight swelling ketone 36 hrs. of not after 36 hrs. exposure testcd of exposure.  
  The preceding example clearly demonstrates the superior solvent resistance of the composition of the present invention, formulation A and B, as compared to the prior art, U.S. Pat. No. 33785! I, formulation C.  
 EXAMPLE 69 An elastomeric silicone composition was poured around a nominal 2V2 threaded malleable iron pipe plug and cured whereby producing an elastomeric mold of the pipe fitting.  
  Employing the procedure of Example l-A, the following composition was poured into the above prepared mold.  
 45 grams of Voranol CP-26O 68 grams of PAP! 50 grams of Propylene carbonate 1 cc of stannous octoate The composition suddenly solidified within about 30 seconds after catalyst addition and after about another 60 seconds, a polyurethane threaded pipe plug was removed from the mold. The cast object, pipe plug, had a density greater than 1 gram/cc.  
 EXAMPLE 70 A 3% inch diameter spur gear was removed from a gear box having a gear and pinion arrangement and an elastomeric silicone mold of said spur gear was prepared.  
  Employing the procedure of Example l-A, the following composition was poured into the mold.  
 60 grams of Voranol CP-26O 60 grams of toluene diisocyanate 30 grams of tetrahydronaphthalene 0.2 cc of lead naphthenate (24% Pb) Within about 25 seconds after catalyst addition, the composition suddenly solidified and a rigid polyurethane spur gear was removed from the mold after the lapse of an additional 45 seconds. The gear had a density of greater than 1 gram/cc.  
 EXAMPLE 71 Prepration of Decorative Article A sheet of polyethylene was vacuum formed over a half relief sculptured horse&#39;s head to yield a thin walled polyethylene mold of said horses head.  
  The following non-flexible urethane composition prepared by the procedure of Example l-A was poured into the mold:  
 45 grams of Voranol CP-260 72 grams of an isocyanate terminated prepolymer prepared from toluene diisocyanate and tetrabromobisphenol A, said prepolymer having an NCO content of 29.4%.  
 30 grams of triethylbenzene 1 cc of lead octoate catalyst.  
  The composition suddenly solidified in about 20 seconds after catalyst addition and within about seconds after catalyst addition a rigid polyurethane replica of the horse head having a density greater than 1 gram/cc was removed from the mold.  
 EXAMPLE 72 In each of the following experiments, all of the components except the catalyst were blended together and then the catalyst was added and blended. The resultant mixture was then poured into a 250 cc polyethylene beaker.  
  The compositions and results are given in the following table. The times were measured from the instant the catalyst was added.  
 EXPERIMENT EXPERIMENT EXPERIMENTC A B Continued EXPERIMENT EXPERIMENT EXPERIMENT C A B (Present (Comparative) (Comparative) Invention) Time for solidification. sec. 3()()*** 72()*** Time solid casting was removed from the mold. sec. N.D.* N.D.*  
 &#34; N.I). not determined. Composition was still liquid after 300 seconds. Composition was still liquid after 720 seconds.  
 &#39; l&#39;he polyol employed was the reaction product of glycerine with propylene oxide to an equivalent weight of about 87.  
 2 &#39;I&#39;DI an PIG/2U mixture of 2.4-/2.h-tolucne diisoeyanatc having an NCO equivalent weight of about 87.  
 EXAMPLE 73 In each of the following experiments, all of the components except the catalyst were blended together and then the catalyst was added and blended. The resultant mixture was then poured into a 250 cc polyethylene beaker.  
  In each of the following experiments, the polyol employed was the reaction product ofglycerine with propylene oxide to an equivalent weight of about 87.  
  In each of the following experiments, the polyisocyanate employed was an 80/20 mixture of 2,442.6- toluene diisocyanate (TDI) having an NCO equivalent weight of about 87.  
  In each of the following experiments acetylene tetrabromide (ATB) was employed as the modifier.  
  In each of the following experiments. the catalysts employed and their designations are as follows:  
 DBTDL dibutyl tin dilaurate CdOc cadmium octoate CoOc l part cobalt octoate dissolved in 2 parts triethyl benzene ZN zinc naphthenate SbOc antimony octoate PMP 1 part phenyl mercuric propionate in 1 part of propylene carbonate.  
  The compositions and results of the experiments are given in the following table.  
 EXPERIMENT NO.  
 77 grams of a polymethylene polyphenylisocyanate having an average functionality of about 2.65 and an NCO equivalent weight of about I35.  
 30 grams of a mixture of the cyclic pentamer and higher cyclic homologs of 1,2-propylene oxide.  
 1 cc of T-9 catalyst (21 stannous octoate catalyst containing 28% tin, 97% of which is tin, commercially available from M &amp; T Chemicals.)  
  The mixture suddenly solidified within about 30 seconds and was demolded within about seconds after catalyst addition. The solid. rigid cast sheet had a density of about 1 g/cc. a Shore D hardness of about and a tensile strength of about 7,346 psi at an elongation of about 12%.  
 We claim:  
  1. A non-elastomeric, non-cellular dense. solid polymer having a density of at least about I gram/cc resulting from admixture of the components of a composition comprising:  
 A. a polymer polyol having from 3 to about 8 hydroxyl groups and a hydroxyl equivalent weight between about 75 and about 230.  
 B. an organic polyisocyanate,  
 C. a liquid modifier compound having a boiling point above about 150C selected from the group consisting of cyclic polyethers and mixtures thereof, said polyethers being cyclic tetramers and above of Polyol, grams 33 33 33 33 33 33 TDI. grams 33 33 33 33 33 33 ATE. grams 2O 20 2O 2O 20 20 DBTDL. cc 0.5 CdOc. cc 0.5 CoOc, cc 0.5 ZN. cc 0.5 SbOc. cc 0.5 PMP. cc 0.5 Time* for solidification. sec. 20 30 2t) 45 4t) 30 Time* solid casting was removed from the mold, sec. 40 60 60 I20 60 Density. g/cc 1.3 1.3 1.3 1.3 L3 1.3  
 * The times were measured from the instant the catalyst was added.  
 EXAMPLE 74 ethylene oxide, propylene oxide, butylene oxide or epichlorohydrin, and  
 D. a non-amine-containing catalyst for urethane formation, which is an organo metal compound;  
 65 wherein Components (A) and (B) are present in amounts so as to provide an NCO:OH ratio of from about 0.8:l to about 2:], Component (C) is present in quantities of from about 20 to about 50 percent with the proviso that when Component (B) is an NCO- containing prepolymer containing less than about 40% NCO by weight. Component (C) is present in quantities of from about to about 50% by weight of the sum of Components (A). (B). and (C); and Component (D) is present in quantities of from about 0.2 to about 10 percent by weight of the sum of the weights of Components (A). (B) and (C); and wherein said polymer can be demolded within less than about 5 minutes, without the application of an external source of heat. after admixture of said composition.  
  2. The composition of claim 1 wherein components (A) and (B) are present in quantities such that the NCOzOH ratio of the (A) and (B) components is from about 0.95:1 to about l.l:l. Component (C) is present in quantities of from about to about 50 percent by weight of the sum of Components (A (B) and (C) and wherein Component (D) is present in quantities of from about 0.5 to about 3 percent by weight of the sum of the weights of Components (A). (B) and (C).  
  3. The composition of claim 2 wherein Component (D) is an organo-metal compound of a metal selected from tin. zinc. lead. mercury. cadmium. bismuth and antimony.  
  4. The composition of claim 3 wherein component (C) is selected from the group consisting of cyclic polyethers of l.2-propylene oxide and of ethylene oxide and mixtures thereof.  
  5. The composition of claim 4 wherein component (C) is selected from the group consisting of cyclic tetramers of ethylene oxide. cyclic tetra&#39;mers of 1.2- propylene oxide, cyclic pentamers of l.2-propylene oxide and mixtures thereof.  
  6. The composition of claim 5 wherein component (D) is an organo-tin compound or an organo-lead compound.  
  7. The articles resulting from casting the compositions of claim 1.  
  8. The articles of claim 9 wherein said articles are furniture components.  
  9. The articles of claim 9 wherein said articles are decorative objects.  
 10. The articles of claim 9 wherein said articles are machine components.