Abstract:
Reaction injection molded polyurethanes prepared from a composition comprising (A) a relatively high molecular weight polyol, (B) a chain extender and (C) a polyisocyanate or polyisothiocyanate are improved by replacing a portion of the relatively high molecular weight polyol with an aminated or partially aminated polyoxyalkylene material.

Description:
CROSS REFERENCE TO RELATED APPLICATION 
     This is a continuation-in-part of application Ser. No. 461,046 filed Jan. 26, 1983 abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     Reaction injection molded polyurethanes are well known in the art as described in a paper entitled &#34;The Bayflex 110 Series--the New Generation of Rim Materials&#34;, by W. A. Ludwico and R. P. Taylor presented at the Society of Automotive Engineers Passenger Car Meeting, Detroit Mich., Sept. 26-30, 1977; a paper entitled &#34;The Properties of High Modulus Rim Urethanes&#34;, by R. M. Gerkin and F. E. Critchfield presented at the above meeting; British Pat. No. 1,534,258 titled &#34;Process for the Production of Elastomeric Polyurethane-Polyurea Moulded Products having a Compact Surface Skin&#34; and a book by F. Melvin Sweeny entitled Introduction to Reaction Injection Molding, Technomics, Inc., 1979. 
     These systems employ, as chain extenders, diols, aromatic amines, cyanoethylated polyoxyalkylene amines and mixtures thereof. 
     It has been thought that as a general rule the aliphatic amines were too fast to be suitably employed in RIM urethane applications. Vanderhider and Lancaster in U.S. Pat. No. 4,269,945 discovered that low molecular weight aliphatic amine compounds could be employed as a part of the chain extender system when employed as a mixture with either or both of such materials as hydroxyl-containing materials and aromatic amines. 
     It has now been discovered that high molecular weight aminated polyols can be employed to enhance certain properties such as one or more of those selected from, for example, flexural modulus, tensile strength, tear strength, and the like in such RIM urethane systems usually without an unacceptable reduction in other properties of the polymer. 
     SUMMARY OF THE INVENTION 
     The present invention pertains to an improvement in molded polymer systems which systems employ a composition which comprises 
     (A) at least one relatively high molecular weight hydroxyl-containing polyol; 
     (B) at least one chain extender; and 
     (C) at least one polyisocyanate, polyisothiocyanate or mixture thereof; 
     the improvement residing in replacing at least a portion of component (A) with, as component (D), a material or mixture of materials having an average equivalent weight of at least 500, preferably from greater than 500 to about 3,000, most preferably from greater than about 500 to about 2,000 and which contains a plurality of oxyalkylene groups and at least one primary or secondary amine group per molecule with the proviso that when such material contains only one primary or secondary amine group per molecule, it also contains at least one other group containing a hydrogen atom reactive with an NCO and/or NCS group per molecule; and wherein: 
     (i) of the total number of hydrogen equivalents contributed by hydroxyl groups and amine groups in components (A), and (D) from about 25 to about 100, preferably from about 50 to about 100, most preferably from about 60 to about 100 percent of the hydrogen equivalents are derived from amine groups; 
     (ii) component (B) is present in quantities of from about 5 to about 400, preferably from about 15 to about 50, most preferably from about 20 to about 40 parts per 100 parts by weight of components (A) and (D); and 
     (iii) the NCX index is from about 0.6 to about 1.5, preferably from about 0.7 to about 1.25 and most preferably from about 0.8 to about 1.10 with the proviso that when the system contains an NCX trimerization catalyst, the NCX index can be as high as about 5. 
     The term NCX index is the ratio of the total number of NCO and/or NCS equivalents to the total number of hydrogen equivalents contained in the formulation. Suitable groups containing hydrogen atoms reactive with NCO and/or NCS groups include, OH, SH, NH and the like. 
     The present invention also concerns a composition comprising: 
     (A) an active hydrogen-containing composition comprising 
     (1) at least one material containing at least one primary or secondary amine group per molecule and has an average equivalent weight of at least 500, preferably from about 500 to about 3000, most preferably from about 500 to about 2000; and 
     (2) optionally a polyol or mixture of polyols whose source of active hydrogen atoms is derived only from groups other than primary or secondary amine groups, has an average active hydrogen equivalent weight of at least 500 suitably from 500 to about 5000, preferably from about 1000 to about 3000, most preferably from about 1500 to about 2500; with the proviso that if polyol (A-1) has only one primary or secondary amine group per molecule, then it also has at least one other group reactive with an NCO and/or NCS group per molecule and wherein in component (A) from about 25 to about 100 percent of the active hydrogen equivalents contained therein are derived from amine groups; and 
     (B) as a chain extender composition, one or more members selected from the group consisting of 
     (1) at least one aliphatic amine-containing material having at least one primary amine group or a mixture of such materials, which material or mixture of materials has an average aliphatic amine hydrogen functionality of from about 2 to about 16, preferably from about 2 to about 12 and most preferably from about 4 to about 8 and an average aliphatic amine hydrogen equivalent weight of from about 15 to 500, preferably from about 40 to about 200 and most preferably from about 60 to about 150; 
     (2) at least one hydroxyl-containing material free of aliphatic amine hydrogen atoms or mixture of such materials, which material or material mixture has an average OH functionality of from about 2 to about 4, preferably from about 2 to about 3, and most preferably about 2; and an average OH equivalent weight of from about 30 to about 120, preferably from about 30 to about 80, and most preferably from about 30 to about 60; 
     (3) at least one aromatic amine-containing compound which is essentially free of aliphatic amine hydrogens and which contains at least 2 aromatic amine hydrogen atoms or a mixture of such materials; and 
     (4) mixtures thereof; and wherein 
     (i) when component (B) has an average equivalent weight of less than about 50, component (B) is present in quantities of from about 5 to about 60, preferably from about 15 to about 50, most preferably from about 20 to about 40 percent by weight of component (A); 
     (ii) when component (B) has an average equivalent weight of from about 50 to about 150, component (B) is present in quantities of from about 5 to about 90, preferably from about 15 to about 70, most preferably from about 20 to about 55 percent by weight of component (A); 
     (iii) when component (B) has an average equivalent weight of greater than about 150, component (B) is present in quantities of from about 5 to about 120, preferably from about 15 to about 100, most preferably from about 20 to about 85 percent by weight of component (A); and 
     (iv) equivalent weight is the average molecular weight divided by the total number of hydrogen atoms attached to an oxygen atom or a nitrogen atom. 
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The relatively high molecular weight hydroxyl-containing compounds which can be employed herein are those polyether polyols, polyester polyols and hydrocarbon derived polyols which are free of active amine hydrogen atoms and which have an average hydroxyl functionality of from about 2 to about 8, preferably from about 2 to about 4 and most preferably from about 2 to about 3 and an average hydroxyl equivalent weight of from about 500 to about 5000, preferably from about 1000 to about 3000 and most preferably from about 1500 to about 2500 including mixtures thereof. 
     Suitable relatively high molecular weight polyether polyols which can be employed herein include those which are prepared by reacting an alkylene oxide, halogen substituted or aromatic substituted alkylene oxide or mixtures thereof with an active hydrogen-containing initiator compound. 
     Suitable such oxides include, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, epichlorohydrin, epibromohydrin, mixtures thereof and the like. 
     Suitable initiator compounds include water, ethylene glycol, propylene glycol, butanediol, hexanediol, glycerine, trimethylol propane, pentaerythritol, hexanetriol, sorbitol, sucrose, hydroquinone, resorcinol, catechol, bisphenols, novolac resins, phosphoric acid, mixtures thereof and the like. 
     Also suitable as initiators for the relatively high molecular weight polyols include, for example, ammonia, ethylenediamine, diaminopropanes, diaminobutanes, diaminopentanes, diaminohexanes, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, ethanolamine, aminoethylethanolamine, aniline, 2,4-toluenediamine, 2,6-toluenediamine, diaminodiphenyloxide(oxydianiline), 2,4&#39;-diaminodiphenylmethane, 4,4&#39;-diaminodiphenylmethane, 1,3-phenylenediamine, 1,4-phenylenediamine, naphthylene-1,5-diamine, triphenylmethane-4,4&#39;,4&#34;-triamine, 4,4&#39;-di(methylamino)diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, 1,3-diethyl-2,4-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,5,3&#39;,5&#39;-tetraethyl-4,4&#39;-diaminodiphenylmethane and amine aldehyde condensation products such as the polyphenyl-polymethylene polyamines produced from aniline and formaldehyde, mixtures thereof and the like. 
     Suitable relatively high molecular weight polyester polyols which may be employed herein include, for example, those prepared by reacting a polycarboxylic acid or anhydride thereof with a polyhydric alcohol. The polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic and/or heterocyclic and may be substituted (e.g. with halogen atom) and/or unsaturated. Examples of carboxylic acids of this kind include succinic acid; adipic acid; suberic acid; azelaic acid; sebacic acid; phthalic acid; isophthalic acid; trimellitic acid; phthalic acid anhydride; tetrahydrophthalic acid anhydride; hexahydrophthalic acid anhydride; tetrachlorophthalic acid anhydride; endomethylene tetrahydrophthalic acid anhydride; glutaric acid anhydride; maleic acid; maleic acid anhydride; fumaric acid; dimeric and trimeric fatty acids; such as oleic acid, which may be in admixture with monomeric fatty acids, terephthalic acid dimethyl ester; terephthalic acid bisglycol ester and the like. Mixtures of such acids or anhydrides may also be employed. 
     Examples of suitable polyhydric alcohols include ethylene glycol, 1,2-propylene glycol; 1,3-propylene glycol; 1,4-, 1,2- and 2,3-butylene glycol; 1,6-hexane diol; 1,8-octane diol; neopentyl glycol; cyclohexane dimethanol(1,4-bis-hydroxymethyl cyclohexane)2-methyl-1,3-propane diol; glycerol; trimethylol propane; 1,2,6-hexane triol; 1,2,4-butane triol; trimethylol ethane; pentaerythritol; quinitol; mannitol; sorbitol; methyl glycoside; diethylene glycol; triethylene glycol; tetraethylene glycol; polyethylene glycol; dipropylene glycol; polypropylene glycols; dibutylene glycol; polybutylene glycols and the like. The polyesters may contain some terminal carboxyl groups. It is also possible to use polyesters of lactones such as caprolactone, or hydroxy carboxylic acids such as hydroxy caproic acid. 
     Suitable high molecular weight polyols also include, hydrocarbon polyols such as, for example, hydroxy terminated polybutadiene rubbers commercially available from Arco Chemical Company as Poly B-D 2000X. 
     Other polyols which can be employed herein include polymer-containing polyols such as, for example, those disclosed in U.S. Pat. No. Re. 29,118 (Stamberger), U.S. Pat. No. Re. 28,715 (Stamberger), U.S. Pat. No. Re. 29,014 (Pizzini et al), U.S. Pat. No. 3,869,413 (Blankenship et al) and U.S. Pat. No. 4,390,645 (Hoffman et al) all of which are incorporated herein by reference. 
     Suitable materials containing amine groups include any of the above mentioned polyols, particularly the polyether polyols, which have been at least partially aminated. Suitable such aminated polyols and method for their preparation are described by Lesene and Godfrey in U.S. Pat. No. 3,161,682; by Speranza in U.S. Pat. No. 3,231,619; by Lee and Winfrey in U.S. Pat. No. 3,236,895; by Hubin and Smith in U.S. Pat. No. 3,436,359; and by Yeakey in U.S. Pat. No. 3,654,370 all of which are incorporated herein by reference. 
     The classical function, utility and definition of chain extenders in polyurethanes are suitably described in U.S. Pat. No. 3,233,025, col. 4, lines 5-28; U.S. Pat. No. 3,915,937, col. 1, lines 20-27 and 36-44; U.S. Pat. No. 4,065,410, col. 1, lines 42-44, col. 2, lines 20-21 and col. 4, line 60 to col. 5, line 41; U.S. Pat. No. 4,048,105, col. 1, lines 30-38 and col. 2, lines 4-13. All of the above are incorporated herein by reference. 
     Suitable hydroxyl-containing chain extenders which are free of aliphatic amine hydrogen atoms include, for example, ethylene glycol, propylene glycol, trimethylol propane, 1,4-butane diol, diethylene glycol, dipropylene glycol, bisphenols, hydroquinone, catechol, resorcinol, triethylene glycol, tetraethylene glycol, dicyclopentadienediethanol, glycerine, low molecular weight ethylene and/or propylene oxide derivatives of glycerine, ethylene diamine, diethylenetriamine, mixtures thereof and the like. 
     Suitable aliphatic amine-containing chain extenders having at least one primary amine group which can be employed herein include, for example, ethylene diamine, 1,3-diaminopropane, 1,4-diaminobutane, isophoronediamine, diethylenetriamine, ethanolamine, aminoethylethanolamine, diaminocyclohexane, hexamethylenediamine, methyliminobispropylamine, iminobispropylamine, bis(aminopropyl)piperazine, aminoethyl piperazine, 1,2-diaminocyclohexane, polyoxyalkyleneamines, bis-(p-aminocyclohexyl)methane, triethylenetetramine, tetraethylenepentamine, mixtures thereof and the like. 
     Particularly suitable are the aminated polyoxypropylene glycols having an average amino hydrogen equivalent weight of from about 60 to about 110. 
     The term aliphatic amine as employed herein includes also the cycloaliphatic amines and heterocyclic aliphatic amines so long as they contain at least one primary amine group. 
     Suitable aromatic amines which can be employed herein as a chain extender which is essentially free of aliphatic amine hydrogen atoms include, for example, 2,4-bis(p-aminobenzyl)aniline, 2,4-diaminotoluene, 2,6-diaminotoluene, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,4&#39;-diaminodiphenylmethane, 4,4&#39;-diaminodiphenylmethane, naphthalene-1,5-diamine, triphenylmethane-4,4&#39;,4&#34;triamine, 4,4&#39;-di-(methylamino)-diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, polyphenyl-polymethylene polyamines, 1,3-diethyl-2,4-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,5,3&#39;,5&#39;-tetraethyl-4,4&#39;-diaminodiphenylmethane, 4,4&#39;-methylene-bis(2,6-diisopropylaniline), mixtures thereof and the like. 
     Use of special mixtures of the chain extenders is fully described by Vanderhider and Lancaster in U.S. Pat. No. 4,269,945 which is incorporated herein by reference. 
     Suitable polyisocyanates include the organic aromatic and aliphatic polyisocyanates, polyisothiocyanates or mixtures thereof. 
     Suitable organic aromatic polyisocyanates which can be employed herein include, for example, any such polyisocyanate having 2 or more NCO groups per molecule such as, for example, 2,4-toluenediisocyanate, 2,6-toluenediisocyanate, p,p&#39;-diphenylmethanediisocyanate, p-phenylenediisocyanate, naphthalenediisocyanate, polymethylene polyphenylisocyanates, mixtures thereof and the like. 
     Also suitable are organic aromatic polyisocyanates and the prepolymers and quasi-prepolymers prepared from such polyisocyanates and compounds having 2 or more active hydrogen atoms. 
     Suitable organic aliphatic polyisocyanates include, in addition to the hydrogenated derivatives of the above mentioned organic aromatic polyisocyanates, 1,6-hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate, 1,4-bis-isocyanatomethyl-cyclohexane, m- or p-tetramethylxylene diisocyanate, mixtures thereof and the like. 
     Also suitable are the corresponding polyisothiocyanates, and NCO or NCS terminated prepolymers or quasi-prepolymers prepared from such polyisocyanates and/or polyisothiocyanates and suitable active hydrogen containing materials. Suitable such prepolymers or quasi-prepolymers include those disclosed by Dominguez et al in U.S. Pat. No. 4,297,444 which is incorporated herein by reference. 
     The polymers can be prepared either in the presence or absence of a catalyst. Those polymers prepared from amine containing polyols do not usually require a catalyst although catalysts can be employed if desired. On the other hand, those polymers prepared from polyols which do not contain nitrogen atoms are prepared in the presence of a catalyst. 
     Suitable catalysts which may be employed herein include, for example, organo-metal compounds, tertiary amines, alkali metal alkoxides, mixtures thereof and the like. 
     Suitable organo-metal catalysts include, for example, organo-metal compounds of tin, zinc, lead, mercury, cadmium, bismuth, antimony, iron, manganese, cobalt, copper, vanadium 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, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin diacetate, ferric acetyl acetonate, lead octoate, lead oleate, phenylmercuric propionate, lead naphthenate, manganese naphthenate, copper naphthenate, vanadyl naphthenate, cobalt octoate, cobalt acetate, copper oleate, vanadium pentoxide, mixtures thereof and the like. 
     Suitable amine catalysts include, for example, triethylenediamine, triethylamine, tetramethylbutanediamine, N,N-dimethylethanolamine, N-ethylmorpholine, bis(2-dimethylaminoethyl)ether, N-methylmorpholine, N-ethylpiperidine, 1,3-bis-(dimethylamino)-2-propanol, N,N,N&#39;,N&#39;-tetramethylethylenediamine, mixtures thereof and the like. 
     Suitable alkali metal alkoxides which can be employed as catalysts for urethane formation include, for example, sodium ethoxide, potassium ethoxide, sodium propoxide, potassium propoxide, sodium butoxide, potassium butoxide, lithium ethoxide, lithium propoxide, lithium butoxide, alkali metal salts of polyols such as described in U.S. Pat. No. 3,728,308, mixtures thereof and the like. 
     Preferably, these urethane catalysts are in liquid form, but if they are inherently a solid at the application temperature, then they may be dissolved in an appropriate liquid, such as, for example, dipropylene glycol. 
     The catalysts, when employed, can be employed in quantities of from about 0.001 to about 5, preferably from about 0.01 to about 1 part per 100 parts of total polyol employed depending upon the activity of the catalyst. Very weak catalysts could possibly be employed in quantities above 5 parts per 100 parts of polyol. 
     Suitable trimerization catalysts which can be employed herein include, for example, the zwitterions disclosed by Kresta and Shen in U.S. Pat. No. 4,111,914 and the tertiary amines, alkali metal salts of lower alkanoic acids, mixtures thereof and the like in U.S. Pat. No. 4,126,741 (Carleton et al) all of which are incorporated herein by reference. 
     The zwitterions can also function as a catalyst for urethane formation i.e. the NCX--OH reaction. 
     If desired, the densities of the polyurethanes produced herein can be reduced by incorporating a blowing agent into the formulation. Suitable such blowing agents are fully described in U.S. Pat. No. 4,125,487 and in U.S. Pat. No. 3,753,933 and so much of these patents as pertain to blowing agents is incorporated herein by reference. Particularly suitable blowing agents include the low boiling halogenated hydrocarbons such as methylene chloride and trichloromonofluoromethane. 
     Another suitable method for reducing the density is by frothing by injecting an inert gas into the mixture of urethane forming components. Suitable such inert gases include, for example, nitrogen, oxygen, carbon dioxide, xenon, helium, mixtures thereof such as air and the like. 
     If desired, cell control agents can be employed, particularly when preparing foams or products of reduced density and/or to assist in paintability of the polyurethane. Suitable cell control agents which can be employed herein include silicone oils such as, for example, DC-193, DC-195, DC-197 and DC-198 commercially available from Dow Corning Corp.; SF-1034, PFA-1635, PFA-1700 and PFA-1660 commercially available from General Electric Co.; and L-520, L-5320 and L-5340 commercially available from Union Carbide Corp.; and B-1048 commercially available from PH. Goldschmidt, AG., mixtures thereof and the like. 
     The polymers of the present invention may additionally contain, if desired, coloring agents, density reducing agents, reinforcing agents, mold release agents, fire retardant agents, fillers, modifiers and the like. 
     Suitable liquid and solid modifiers are disclosed and described in U.S. Pat. Nos. 4,000,105 and 4,154,716 and so much thereof as pertains to suitable modifier substances are incorporated herein by reference. However, any such modifier described therein which fulfills the definition of any of the other components as described in this application are not considered as modifiers but rather as one of the components of the present invention. 
     Particularly suitable as the modifier or filler substances are fiberglass reinforcement fibers, particularly those having lengths of from about 1/16 inch (0.16 cm) to about 1/2 inch (1.27 cm) and milled glass fibers having a maximum length of 1/16 inch (0.16 cm), 1/8 inch (0.32 cm) or 1/4 inch (0.64 cm) and the like. Other particularly suitable fillers are mica, wollastonite, fumed silica, and the like. 
     The components which react to form the polyurethanes of the present invention can be shaped or formed into useful articles by injecting the reactive mixture into molds which are capable of withstanding the exotherm of the polymerizing mass and are non-reactive with and are insoluble when in contact with the liquid reactive mixture. Particularly suitable molds are those made of metal such as aluminum, copper, brass, steel and the like. In some instances non-metal molds can be employed such as those made of, for example, polyethylene, polypropylene, polyethylene terephthalate, silicone elastomers and the like. 
     Particularly suitable injection methods for the RIM applications of the present invention include those disclosed in the aforementioned articles by Ludwico et al, Gerkin et al, British Pat. No. 1,534,258 and the book by F. Melvin Sweeney all of which are incorporated herein by reference. 
     To prevent the solidifying mass from adhering to the mold surface, it may be necessary to precoat the mold surface with a film of a suitable mold release agent such as, for example, hydrocarbon wax or a polysiloxane preparation or a polytetrafluoroethylene coating, or employ an internal mold release agent in the composition. 
     When injecting a relatively rapid-setting blend into massive metal molds, it may be necessary for rapid demolding to preheat the molds to an appropriate temperature so that the mold will not abstract the heat of polymerization from the reactive mass and inappropriately delay the solidification time expected of a given formulation. On the other hand, thin wall metal molds could exhibit a minimal &#34;heat sink&#34; effect on relatively large cross section castings and thus, these thin wall metal molds may not require preheating. 
     The following examples are illustrative of the present invention and are not to be construed as to limiting the scope thereof in any manner. 
     The term polyol which follows means those materials having hydrogen atoms attached to an oxygen or nitrogen atom. 
     The term total hydrogen equivalent weight means the value derived from dividing the average molecular weight by the total number of hydrogen atoms attached to an oxygen atom and/or a nitrogen atom. 
     Following is a list of materials employed in the examples and comparative experiments. 
     POLYOL A is the reaction product of glycerine and propylene oxide at a molar ratio of about 1 to 6 respectively and having an equivalent weight of about 150. 
     POLYOL B is the reaction product of polyol A and propylene oxide and subsequently end-capped with about 18% ethylene oxide by weight. The polyol has an OH equivalent weight of about 1598. 
     POLYOL C is an aminated polyoxypropylene glycol having an average molecular weight of about 2000 and an average total amine hydrogen equivalent weight of about 500 which is commercially available from Texaco Chemicals as JEFFAMINE D-2000. 
     POLYOL D is a polyoxypropylene glycol having an average hydroxyl equivalent weight of about 1000. 
     POLYOL E is an aminated polyoxypropylene triol having an average molecular weight of about 5000 and a degree of amination of about 82 percent. This polyol has an average total hydrogen equivalent weight of about 991. 
     POLYOL F is an aminated polyoxypropylene triol having an average molecular weight of about 5000 and a degree of amination of about 30 percent. This polyol has an average total hydrogen equivalent weight of about 1250. 
     POLYOL G is an aminated polyoxypropylene triol having an average molecular weight of about 5000 and a degree of amination of about 50 percent. This polyol has an average total hydrogen equivalent weight of about 1111. 
     POLYOL H is the reaction product of polyol A and propylene oxide and subsequently end-capped with about 14% ethylene oxide by weight. This product has an average OH equivalent weight of about 1598. 
     CHAIN EXTENDER A is ethylene glycol which has an average hydroxyl equivalent weight of 31. 
     CHAIN EXTENDER B is diethyltoluenediamine having an average total amine hydrogen equivalent weight of 44.5 commercially available from Mobay as E-505. 
     POLYISOCYANATE A is a uretoneimine modified 4,4&#39;-diphenylmethane diisocyanate having an average NCO equivalent weight of about 143, commercially available from Rubicon Chemicals Incorporated as RUBINATE LF-168. 
     POLYISOCYANATE B is a quasi-prepolymer prepared from 4,4&#39;-diphenylmethane diisocyanate and a low molecular weight propylene glycol diol having an average NCO equivalent weight of about 179. This material is commercially available from Rubicon Chemicals Incorporated as Rubinate LF-179. 
     CATALYST A is an organotin catalyst commercially available from Witco Chemical as FOMREZ UL-28. 
     CATALYST B is a 33% solution triethylene diamine in dipropylene glycol commercially available from Air Products as DABCO 33LV. 
     CATALYST C is lead octoate commercially available from Tenneco as Nenodex. 
     CATALYST D is an organotin catalyst, dibutyltin dilaurate, available from M&amp;T Chemical Co. as T-12. 
    
    
     The following examples and comparative experiments were prepared by the following general procedure. 
     The components commonly referred to as the B-side which includes the active hydrogen-containing materials and catalyst were added to a tank referred to as the polyol tank in the ratios indicated and mixed and maintained at the indicated temperature. The isocyanate component usually referred to as the A-side was added to an isocyanate tank in the indicated proportion and maintained at the indicated temperature. The machine and mold conditions employed to convert the components into a molded polyurethane are given in the following table. 
     
                                           TABLE__________________________________________________________________________Component,   Example or Comparative ExperimentCondition,   Comp.and Physical Expt.  Example                      Example                             Example                                    ExampleProperty     A      1      2      3      4__________________________________________________________________________Polyol B, pbw.sup.1        100    75     50     25     --Polyol C, pbw.sup.1        --     25     50     75     100Polyol D, pbw.sup.1        --     --     --     --     --Chain Extender A, pbw.sup.1        10     10     10     10     10Chain Extender B, pbw.sup.1        --     --     --     --     --Polyisocyanate A, pbw.sup.1        56.55  61.73  66.89  72.06  77.24Catalyst A, %.sup.2        0.10   0.10   0.05   0.05   0.05Catalyst B, %.sup.2        0.10   0.10   0.05   0.05   0.05Catalyst C, %.sup.2        --     --     --     --     --NCX INDEX.sup.5        1.03   1.03   1.03   1.03   1.03MOLD Temp.,°F.   159    160    156    159    159°C.   70.5   71.1   68.9   70.5   70.5Polyol pressure, psi        2,000  2,000  2,000  2,000  2,000Polyol pressure, bar        --     --     --     --     --Polyol pressure, kPa        13,790 13,790 13,790 13,790 13,790Isocyanate pressure, psi        2,000  2,000  2,000  2,000  2,000Isocyanate pressure, bar        --     --     --     --     --Isocyanate pressure, kPa        13,790 13,790 13,790 13,790 13,790Polyol Temp.,°F.   98     104    84     84     82°C.   36.7   40.0   28.9   28.9   27.8Polyisocyanate Temp.,°F.   96     100    88     86     86°C.   35.6   37.8   31.1   30.0   30.0Through-put, g/sec.        206    239    243    246    248Machine      ADMIRAL.sup.4               ADMIRAL.sup.4                      ADMIRAL.sup.4                             ADMIRAL.sup.4                                    ADMIRAL.sup.4Post Cure Temp.,°F.   250    250    250    250    250°C.   121.1  121.1  121.1  121.1  121.1Post Cure Time,min.         60     60     60     60     60sec.         3600   3600   3600   3600   3600Tensile Strength,psi          1523   2471   2513   2906   2815kPa          10,500 17,037 17,326 20,036 19,408Elongation, %        198    278    262    294    274Flexural Modulus,psi          3,338  5,387  6,140  7,583  8,371kPa          23,014 37,142 42,333 52,283 57,716Die C Tear Strength,pli          262    372    377    466    485kg/m         4,678  6,642  6,731  8,267  8,660__________________________________________________________________________Component,   Example or Comparative ExperimentCondition,   Comp.and Physical Expt.  Example                      Example                             Example                                    ExampleProperty     B      5      6      7      8__________________________________________________________________________Polyol B, pbw.sup.1        100    75     50     25     --Polyol C, pbw.sup.1        --     25     50     75     100Polyol D, pbw.sup.1        --     --     --     --     --Chain Extender A, pbw.sup.1        20     20     20     20     20Chain Extender B, pbw.sup.1        --     --     --     --     --Polyisocyanate A, pbw.sup.1        104.24 109.41 114.57 119.74 124.92Catalyst A, %.sup.2        0.15   0.05   0.05   0.05   0.05Catalyst B, %.sup.2        0.10   0.05   0.05   0.05   0.05Catalyst C, %.sup.2        --     --     --     --     --NCX INDEX.sup.5        1.03   1.03   1.03   1.03   1.03MOLD Temp.,°F.   170    161    158    159    158°C.   76.7   71.7   70.0   70.6   70.0Polyol pressure, psi        2,000  2,000  2,000  2,000  2,000Polyol pressure, bar        --     --     --     --     --Polyol pressure, kPa        13,790 13,790 13,790 13,790 13,790Isocyanate pressure, psi        2,000  2,000  2,000  2,000  2,000Isocyanate pressure, bar        --     --     --     --     --Isocyanate pressure, kPa        13,790 13,790 13,790 13,790 13,790Polyol Temp.,°F.   100    104    85     86     88°C.   37.8   40.0   29.4   30.0   31.1Polyisocyanate Temp.,°F.   98     100    88     87     90°C.   36.7   37.8   31.1   30.6   32.2Through-put, g/sec.        254    289    296    301    298Machine      ADMIRAL.sup.4               ADMIRAL.sup.4                      ADMIRAL.sup.4                             ADMIRAL.sup.4                                    ADMIRAL.sup.4Post Cure Temp.,°F.   250    250    250    250    250°C.   121.1  121.1  121.1  121.1  121.1Post Cure Time,min.         60     60     60     60     60sec.         3600   3600   3600   3600   3600Tensile Strength,psi          3104   4017   4093   4344   4302kPa          21,401 27,696 28,220 29,950 29,661Elongation, %        210    256    236    224    190Flexural Modulus,psi          24,513 35,926 35,981 45,608 49,900kPa          169,011               247,702                      248,081                             314,457                                    344,049Die C Tear Strength,pli          559    657    669    749    747kg/m         9,981  11,731 11,946 13,374 13,338__________________________________________________________________________Component,   Example or Comparative ExperimentCondition,   Comp.and Physical Expt.  Example                      Example                             Example                                    ExampleProperty     C      9      10     11     12__________________________________________________________________________Polyol B, pbw.sup.1        100    75     50     25     --Polyol C, pbw.sup.1        --     25     50     75     100Polyol D, pbw.sup.1        --     --     --     --     --Chain Extender A, pbw.sup.1        30     30     30     30     30Chain Extender B, pbw.sup. 1        --     --     --     --     --Polyisocyanate A, pbw.sup.1        151.9  157.09 162.25 162.54 167.57Catalyst A, %.sup.2        0.15   0.10   0.075  0.05   0.05Catalyst B, %.sup.2        0.10   0.10   0.05   0.05   0.05Catalyst C, %.sup.2        --     --     --     --     --NCX INDEX.sup.5        1.03   1.03   1.03   1.03   1.03MOLD Temp.,°F.   169    156    157    159    158°C.   76.1   68.9   69.4   70.6   70.0Polyol pressure, psi        2,000  2,000  2,000  2,000  2,000Polyol pressure, bar        --     --     --     --     --Polyol pressure, kPa        13,790 13,790 13,790 13,790 13,790Isocyanate pressure, psi        2,000  2,000  2,000  2,000  2,000Isocyanate pressure, bar        --     --     --     --     --Isocyanate pressure, kPa        13,790 13,790 13,790 13,790 13,790Polyol Temp.,°F.   104    88     79     87     88°C.   40.0   31.1   26.1   30.6   31.1Polyisocyanate Temp.,°F.   100    92     84     89     90°C.   37.8   33.3   28.9   31.7   32.2Through-put, g/sec.        272    273    269    265    270Machine      ADMIRAL.sup.4               ADMIRAL.sup.4                      ADMIRAL.sup.4                             ADMIRAL.sup.4                                    ADMIRAL.sup.4Post Cure Temp.,°F.   250    250    250    250    250°C.   121.1  121.1  121.1  121.1  121.1Post Cure Time,min.         60     60     60     60     60sec.         3600   3600   3600   3600   3600Tensile Strength,psi          3931   3965   4600   5094   4858kPa          27,103 27,337 31,716 35,122 33,494Elongation, %        170    120    140    170    140Flexural Modulus,psi          58,073 74,215 84,456 94,008 101,457kPa          400,400               511,696                      582,305                             648,164                                    699,524Die C Tear Strength,pli          716    752    898    934    911kg/m         12,785 13,428 16,035 16,678 16,267__________________________________________________________________________Component,   Example or Comparative ExperimentCondition,   Comp.and Physical Expt.  Example                      Example                             Example                                    ExampleProperty     D      13     14     15     16__________________________________________________________________________Polyol B, pbw.sup.1        100    75     50     25     --Polyol C, pbw.sup.1        --     25     50     75     100Polyol D, pbw.sup.1        --     --     --     --     --Chain Extender A, pbw.sup.1        20     20     20     20     20Chain Extender B, pbw.sup.1        --     --     --     --     --Polyisocyanate A, pbw.sup.1        91.89  96.46  101.01 105.56 110.14Catalyst A, %.sup.2        0.10   0.10   0.05   0.05   0.05Catalyst B, %.sup.2        0.10   0.10   0.05   0.05   0.05Catalyst C, %.sup.2        --     --     --     --     --NCX INDEX.sup.5        0.91   0.91   0.91   0.91   0.91MOLD Temp.,°F.   144    162    158    156    158°C.   62.2   72.2   70.0   68.9   70.0Polyol pressure, psi        2,000  2,000  2,000  2,000  2,000Polyol pressure, bar        --     --     --     --     --Polyol pressure, kPa        13,790 13,790 13,790 13,790 13,790Isocyanate pressure, psi        2,000  2,000  2,000  2,000  2,000Isocyanate pressure, bar        --     --     --     --     --Isocyanate pressure, kPa        13,790 13,790 13,790 13,790 13,790Polyol Temp.,°F.   98     102    85     85     85°C.   36.7   38.9   29.4   29.4   29.4Polyisocyanate Temp.,°F.   96     100    88     87     87°C.   35.6   37.8   31.1   30.6   30.6Through-put, g/sec.        257    290    279    279    285Machine      ADMIRAL.sup.4               ADMIRAL.sup.4                      ADMIRAL.sup.4                             ADMIRAL.sup.4                                    ADMIRAL.sup.4Post Cure Temp.,°F.   250    250    250    250    250°C.   121.1  121.1  121.1  121.1  121.1Post Cure Time,min.         60     60     60     60     60sec.         3600   3600   3600   3600   3600Tensile Strength,psi          2989   3435   4078   4106   4424kPa          20,608 23,683 28,116 28,309 30,502Elongation, %        210    252    268    422    276Flexural Modulus,psi          14,614 26,689 29,900 37,528 38,962kPa          100,760               184,014                      206,154                             258,747                                    268,634Die C Tear Strength,pli          446    562    676    759    786kg/m         7,964  10,035 12,071 13,553 14,035__________________________________________________________________________Component,   Example or Comparative ExperimentCondition,   Comp.and Physical Expt.  Example                      Example                             Example                                    ExampleProperty     E      17     18     19     20__________________________________________________________________________Polyol B, pbw.sup.1        100    75     50     25     --Polyol C, pbw.sup.1        --     25     50     75     100Polyol D, pbw.sup.1        --     --     --     --     --Chain Extender A, pbw.sup.1        30     30     30     30     30Chain Extender B, pbw.sup.1        --     --     --     --     --Polyisocyanate A, pbw.sup.1        138.92 143.65 148.37 153.10 157.81Catalyst A, %.sup.2        0.15   0.10   0.05   0.05   0.05Catalyst B, %.sup.2        0.10   0.10   0.05   0.05   0.05Catalyst C, %.sup.2        --     --     --     --     --NCX INDEX.sup.5        0.94   0.94   0.94   0.94   0.94MOLD Temp.,°F.   170    156    157    159    158°C.   76.7   68.9   69.4   70.6   70.0Polyol pressure, psi        2,000  2,000  2,000  2,000  2,000Polyol pressure, bar        --     --     --     --     --Polyol pressure, kPa        13,790 13,790 13,790 13,790 13,790Isocyanate pressure, psi        2,000  2,000  2,000  2,000  2,000Isocyanate pressure, bar        --     --     --     --     --Isocyanate pressure, kPa        13,790 13,790 13,790 13,790 13,790Polyol Temp.,°F.   100    88     84     86     88°C.   37.8   31.1   28.9   30.0   31.1Polyisocyanate Temp.,°F.   98     92     86     84     90°C.   36.7   33.3   30.0   28.9   32.2Through-put, g/sec.        283    282    282    270    277Machine      ADMIRAL.sup.4               ADMIRAL.sup.4                      ADMIRAL.sup.4                             ADMIRAL.sup.4                                    ADMIRAL.sup.4Post Cure Temp.,°F.   250    250    250    250    250°C.   121.1  121.1  121.1  121.1  121.1Post Cure Time,min.         60     60     60     60     60sec.         3600   3600   3600   3600   3600Tensile Strength,psi          3560   3742   4468   5093   4857kPa          24,545 25,800 30,805 35,115 33,487Elongation, %        170    130    170    216    150Flexural Modulus,psi          47,971 66,101 80,582 92,051 95,035kPa          330,749               455,752                      555,595                             634,671                                    655,245Die C Tear Strength,pli          637    716    912    972    1027kg/m         11,374 12,785 16,285 17,356 18,338__________________________________________________________________________Component,   Example or Comparative ExperimentCondition,   Comp.        Comp.       Comp.and Physical Expt. Example                     Expt.                          Example                                 Expt.                                      ExampleProperty     F     21     G    22     H    23__________________________________________________________________________Polyol B, pbw.sup.1        --    --     --   --     --   --Polyol C, pbw.sup.1        --    100    --   100    --   100Polyol D, pbw.sup.1        100   --     100  --     100  --Chain Extender A, pbw.sup.1        20    20     30   30     --   --Chain Extender B, pbw.sup.1        --    --     --   --     22   22Polyisocyanate A, pbw.sup.1        110.14              124.92 157.80                          167.57 51.32                                      59.94Catalyst A, %.sup.2        0.20  0.05   0.20 0.05   0.20 0Catalyst B, %.sup.2        0.10  0.05   0.10 0.05   --   0Catalyst C, %.sup.2        0.20  --     0.20 --     0.10 0NCX INDEX.sup.5        1.03  1.03   1.03 1.03   0.60 0.60MOLD Temp.,°F.   160   158    160  158    160  160°C.   71.1  70.0   71.1 70.0   71.1 71.1Polyol pressure, psi        --    2,000  --   2,000  --   --Polyol pressure, bar        150   --     150  --     150  150Polyol pressure, kPa        --    --     --   --     --   --Isocyanate pressure, psi        --    2,000  --   2,000  --   --Isocyanate pressure, bar        150   --     150  --     150  150Isocyanate pressure, kPa        15,000              13,790 15,000                          13,790 15,000                                      15,000        °F.? 107? 88? 103? 88? 90? 100? °C.? 41.7? 31.1? 39.4? 31.1? 32.2? 37.8? Polyisocyanate Temp.,? °F.? 96? 90? 92? 90? 100? 103? °C.? 35.6? 32.2? 33.3? 32.2? 37.8? 39.4? Through-put, g/sec.? 1000? 298? 1000? 270? 1000? 1000? Machine? KM.sup.3? ADMIRAL.sup.4? KM.sup.3? ADMIRAL.sup.4? KM.sup.3? KM.sup.3? Post Cure Temp.,? °F.? 250? 250? 250? 250? 250? 250? °C.? 121.1? 121.1? 121.1? 121.1? 121.1? 121.1? Post Cure Time,? min.? 60? 60? 60? 60? 60? 60? sec.? 3600? 3600? 3600? 3600? 3600? 3600? Tensile Strength,? psi? 3206? 4302? 3107? 4858? 1724? 4525? kPa? 22,104? 29,661? 21,422? 33,494? 11,886? 31,198? Elongation, %? 200? 190? 96? 140? 255? 272? Flexural Modulus,? psi? 15,116? 49,900? 37,382?101,457? 9,236? 40,072? kPa? 104,221? 344,049? 257,740? 699,524? 63,680? 276,287? Die C Tear Strength,? pli? 453? 747? 433? 911? 366? 773? kg/m? 8,089? 13,338? 7,731? 16,267? 6,535? 13,803? Component, Example or Comparative Experiment Condition, Comp. ? ? ? and Physical Expt. Example Example Example Property I 24 25 26? Polyol E, pbw.sup.1 --? --? --? 100 Polyol F, pbw.sup.1 --? 100 --? --? Polyol G, pbw.sup.1 --? --? 100 --? Polyol H, pbw.sup.1 100 --? --? --? Chain Extender A, pbw.sup.1 --? --? --? --? Chain Extender B, pbw.sup.1 18 18 18 18 Polyisocyanate B, pbw.sup.1 48.6 48.6 48.6 55.2 Catalyst A, %.sup.2 0.10 0.10 0.10 --? Catalyst B, %.sup.2 0.10 --? --? --? Catalyst C, %.sup.2 --? --? --? --? Catalyst D, %.sup.2 --? 0.10 0.10 --? NCX INDEX.sup.5 1.03 0.98 0.93 1.03 MOLD Temp., °F. 145 145 145 145 °C. 62.7 62.7 62.7 62.7 Polyol pressure, psi 2,000 2,000 2,000 2,400 Polyol pressure, bar --? --? --? --? Polyol pressure, kPa 13,790 13,790 13,790 16,552 Isocyanate pressure, psi 2,000 2,000 2,000 2,400 Isocyanate pressure, bar --? --? --? --? Isocyanate pressure, kPa 13,790 13,790 13,790 16,552 Polyol Temp.,  °F. 100 100 100 124 °C. 37.8 37.8 37.8 51.1 Polyisocyanate Temp., °F. 100 100 100 122 °C. 37.8 37.8 37.8 50 Through-put, g/sec. 215 206 207 215 Machine ADMIRAL.sup.4 ADMIRAL.sup.4 ADMIRAL.sup.4 ADMIRAL.sup.4 Post Cure Temp., °F. 250 250 250 250 °C. 121.1 121.1 121.1 121.1 Post Cure Time, min. 60 60 60 60 sec. 3600 3600 3600 3600 Tensile Strength,  psi 2532 2815 2466 3375 kPa 17,462 19,828 17,007 23,276 Elongation, % 278 488 320 320 Flexual Modulus, psi 9,312 11,544 15,515 19,814 kPa 64,221 79,614 107,000 136,648 Die C Tear Strength, pli 378 512 500 418 kg/m 6,756 9,151 8,937 7,471?