Abstract: An improved process for the preparation of thermoplastic polyurethane elastomers by a one-shot reaction of an organic diisocyanate, a polymeric diol, and a diol extender is disclosed wherein the diol components, either singly or together, are treated with a trivalent phosphorus compound prior to their reaction with the diisocyanate in the presence of a stannous tin urethane catalyst. The process when carried out with pure urethane grade diol components results in very efficient catalysis which in turn requires lower levels of stannous tin catalyst than would otherwise be employed. Moreover, the process can be carried out with diol components that are not urethane grade materials but which are contaminated by high levels of peroxidic impurities and which materials would otherwise be useless for the preparation of high grade elastomer products.

Abstract: Isopropylphenyl esters are converted to di- or trihydric phenols via a novel autoxidation of the esters at high conversion rates to the corresponding hydroperoxyisopropylphenyl esters in the presence of a catalyst combination comprising at least two members selected from the group consisting of (i) a metal phthalocyanine; (ii) a di-tertiary alkyl peroxide; and (iii) a tertiary alkyl hydroperoxide.Rearrangement of the hydroperoxyisopropylphenyl esters to the corresponding hydroxyphenyl esters and the hydrolysis of the latter compounds provides the phenols in overall yields (from the starting esters) heretofore not obtainable. Novel bis(hydroperoxyisopropylphenyl)carbonates are described which are attractive intermediates for the intermediate bisphenol carbonate or the final hydroquinone hydrolysis product.

Abstract: An improved process is described for the reaction of an isocyanate (mono or poly) with a carboxylic acid or anhydride (mono or poly) to form the corresponding imide, amide or amide-imides. The improvement lies in using as the catalyst the 1-oxide, 1-sulfide or 1-hydrocarbylimino derivative of a phospholene, phospholane or phosphetane. The latter compounds are also substituted in the 1-position by a hydrocarbyl (C.sub.1-12) or halohydrocarbyl (C.sub.1-12) and may additionally carry one or more halo, lower-alkoxy, phenoxy, lower-hydrocarbyl or halo-substituted hydrocarbyl groups on the ring carbon atoms.

Abstract: A novel process is disclosed for the preparation of cyclic ureas having the formula ##STR1## wherein A is a straight chain alkylene radical of 2 to 4 carbon atoms, inclusive, wherein said alkylene radical can be substituted by at least one member selected from the group consisting of halogen, lower alkyl, lower alkoxy, aryl, aryloxy, aralkyl, and cycloaklyl. An alkylene diamine having the formula NH.sub.2 ANH.sub.2, wherein A is defined as above, is reacted in a solvent with carbonyl sulfide to form the corresponding N-(.omega.-aminoalkyl)thiocarbamic acid (NH.sub.2 ANHCOSH) or zwitterion thereof. The thiocarbamic acid is then heated to form the cyclic urea.The cyclic ureas are useful as cross-linkers and extenders in polyurethane formulations, and those ureas having 4 carbons in the alkylene chain find particular utility in the production of bis cyclic ureas which serve as masked isocyanate compounds in one-component polyurethane elastomer formulations.

Abstract: Color stabilized isocyanates, particularly methylene-bridged aromatic isocyanates [methylenebis(phenyl isocyanate) and prepolymers thereof], are derived by incorporating in the isocyanate a color stabilizing amount of a compound of the formula ##STR1## wherein R.sub.1 =alkyl, aryl; R.sub.2 =alkyl; R.sub.3 =H, alkyl or aralkyl; and R.sub.1 and R.sub.2 taken together represent the residue of an oxazoline or oxazine. 2-Ethyloxazoline is a preferred color stabilizing compound. The above compounds can also be used to discharge undesirable colors which have developed in such isocyanates on storage.

Abstract: The reactivity of polymethylene polyphenyl isocyanates containing 20 to 90 percent of methylenebis(phenyl isocyanates) is improved, and stabilized against a decline on storage, by incorporating therein very small amounts of a compound of the formula ##STR1## wherein R.sub.1 =alkyl, aryl; R.sub.2 =alkyl; R.sub.3 =H, alkyl or aralkyl; and R.sub.1 and R.sub.2 taken together represent the residue of an oxazoline or oxazine. 2-Ethyloxazoline is the preferred compound for incorporation in the polyisocyanate.

Abstract: A process is described for converting organic polyisocyanates to carbodiimide-containing polyisocyanates by heating said organic polyisocyanates in the presence of an organoarsine-substituted polystyrene carbodiimide-forming catalyst until a desired level of conversion is achieved, followed by separation of catalyst from product. It is thus possible to obtain a carbodiimide-containing polyisocyanate which is free from catalyst and hence free from the possibility that carbodiimide formation can continue on storage of the product. In a particular embodiment the process is employed to convert methylenebis(phenyl isocyanate), which is normally solid at ambient temperatures, to a storage stable liquid product. The polymeric catalysts employed in the process are characterized by a recurring unit of the formula: ##STR1## wherein R.sub.1 and R.sub.2 are hydrocarbyl, R.sub.3 is hydrogen, chloro or methyl, R.sub.4 is hydrogen or methyl and n is 0 or 1.

Abstract: Storage stable aqueous solutions derived from polymethylene polyphenyl polyisocyanates are described, which solutions are useful as sealant coating compositions for wood and other substrates and, in the form of emulsions with polyisocyanates, as improved particle board binders. The storage stable aqueous solutions are obtained by admixing polymethylene polyphenyl polyisocyanates with less than a stoichiometric amount of a polyethylene glycol (MW 600 to 3000) or polypropylene glycol tipped with 15 to 85 percent ethylene oxide (MW 1000 to 3500) and, within a short time of completing the admixture but during the period where said mixture is completely soluble in water, dissolving said mixture in water. Optionally, a difunctional extender is added to the resulting solution in amount less than that required to react with all the isocyanate groups.

Abstract: Novel bis cyclic ureas are disclosed having the formula ##STR1## WHEREIN C.sub.n H.sub.2 n represents alkylene from 4 to 12 inclusive and provided there are at least 4 carbon atoms in succession in the chain and R is the residue obtained by the removal of both halogen atoms from a diacid halide.The bis cyclic ureas are easily converted to a novel class of aliphatic diisocyanates simply by heating. Alternatively, they are blended with polymeric polyols to form one-component storage stable compositions which are thermally converted to polyurethane resins without any significant volatile or side product formation.

Abstract: Modified polystyrenes are described which are catalysts for the conversion of organic isocyanates to the corresponding carbodiimides. The modified polystyrenes are characterized by the presence of recurring units of the formula: ##STR1## R.sub.1 and R.sub.2 are hydrocarbyl which is free of substituents reactive with isocyanate groups, R.sub.3 is hydrogen, chloro or methyl, R.sub.4 is hydrogen or methyl, and n is 0 or 1.The use of the above polymers to catalyze the formation of carbodiimides from organic isocyanates is also disclosed.

Abstract: Substantially linear, segmented polyester amides are described which contain aromatic residues in the "hard" segments but which still possess sufficiently low melt properties to be injection moldable. The polyester amides are obtained by reacting a carboxylic acid-terminated prepolymer (derived by reacting an excess of a dicarboxylic acid with a polymeric diol of molecular weight 400 to 4000) with a stoichiometric amount of methylenebis(phenyl isocyanate) or toluene diisocyanate or mixtures of these isocyanates and, optionally, a dicarboxylic acid.

Abstract: A process and apparatus are described for the preparation of continuous polymer foam bunstock having substantially rectangular cross-section. The novel feature comprises a panel member having its downstream end pivotally mounted above a conventional moving trough-shaped mold, the underside of said panel member floating freely in tangential contact with the rising foam in the area immediately following the gel point of said foam but before the point at which the foam is no longer sufficiently mobile to be molded without distortion of the cells thereof.

Abstract: Novel solid polyisocyanurate polymers are disclosed which comprise the reaction product of an organic polyisocyanate, a trimerization catalyst and a polyol combination comprising from about 0.025 to about 0.15 equivalent and about 0.05 to about 0.25 equivalent, per equivalent of polyisocyanate, respectively of a polypropyleneoxy triol having an equivalent weight of from about 750 to about 1500 and ethylene glycol.Although containing a higher proportion of polyurethane linkages than those polyisocyanurates containing the polypropyleneoxy triol alone, the polymers of the invention are characterized by superior high temperature resistance and are particularly useful in the preparation of high modulus molded parts using reaction injection molding (RIM) techniques.

Abstract: Novel solid polyisocyanurate polymers are disclosed which comprises the reaction product of an organic polyisocyanate, a trimerization catalyst and a polyol combination comprising from about 0.025 to about 0.15 equivalent and about 0.05 to about 0.25 equivalent, per equivalent of polyisocyanate, respectively of an ethylene oxide capped polypropyleneoxy glycol having an equivalent weight of from about 750 to about 1500 and either 1,4-butanediol or diethylene glycol.Although containing a higher proportion of polyurethane linkages than those polyisocyanurates containing the polypropyleneoxy glycol alone, the polymers of the invention are characterized by superior high temperature resistance and are particularly useful in the preparation of high modulus molded parts using reaction injection molding (RIM) techniques.

Abstract: An improved process for the nitration of aromatic hydrocarbons is described. The aromatic hydrocarbon (benzene, toluene of particular interest) is reacted with gaseous nitrogen dioxide in the presence of a catalytic amount of sulfuric acid and in the absence of oxygen. The process is highly selective and avoids the formation of undesired by-products. The acid employed as catalyst can be recovered and recycled after removal of water of condensation liberated in the reaction.

Abstract: Novel solvent soluble and injection moldable copolyamideimides are disclosed that are characterized in that from about 30 percent to about 70 percent of the recurring units are ##STR1## and in the remaining 30-70 percent of the recurring units are ##STR2## wherein C.sub.n H.sub.2n represents alkylene from 7 to 12 carbon atoms, inclusive, and Ar is ##STR3## where X = --SO.sub.2 --, --CO--, --O--, or alkylene (C.sub.1-4). The copolyamideimides are further characterized by ease of melt processing such as by extruding or injection molding while at the same time prossessing good high temperature stability and unexpectedly high impact and tensile yield strengths.

Abstract: Novel stabilized polyhalogenated polyol blends are disclosed which include in the blend a catalytic amount of a tertiary amine urethane catalyst and a stabilizing amount of a particular diepoxide. The polyol blends retain the same catalytic reactivity for reaction with organic polyisocyanates to form polyurethane foams over extended storage periods and are also stable with respect to blend viscosity. The polyurethane foams prepared from the stabilized polyol blends are characterized by excellent flame resistance and low smoke evolution when tested according to the ASTM E-84 test. The stabilized polyol blends provide an efficient means for reducing the number of polyurethane forming components or streams that need be stored, handled, or pumped to a polyurethane foam mixing apparatus.

Abstract: Bis(2-hydroxyalkyl) N,N-di(lower-alkyl)aminomethylphosphonates are described. These phosphorus-containing polyols can be incorporated into polyurethane foams to render the latter fire retardant. They have the advantage over closely related phosphorus-containing polyols that they are autocatalytic in the polyurethane foam forming reaction and that they can be mixed with the polyol component of the polyurethane foam forming composition to give a mixture (premix) which can be maintained in storage for prolonged periods without showing any signs of deterioration.

Abstract: Random copolymers of polyparabanic acids and polyamide-imides are described. The copolymers are highly useful engineering thermoplastics which, unlike the corresponding polyparabanic acid homopolymers, are readily moldable by compression molding and like techniques. The copolymers are readily prepared by the one-shot reaction of bis(alkoxyoxalyl)amides of aliphatic, araliphatic or aromatic diamines, with organic diisocyanates and trimellitic anhydride.

Abstract: Modified polystyrenes are described which are catalysts for the conversion of organic isocyanates to the corresponding carbodiimides. The modified polystyrenes are characterized by the presence of recurring units of the formula: ##STR1## WHEREIN THE BROKEN LINES IN THE PHOSPHOLENE NUCLEUS INDICATE A DOUBLE BOND LOCATED BETWEEN THE CARBON ATOM AT POSITION 3 AND ONE OF THE CARBON ATOMS AT POSITIONS 2 AND 4, THE H atom is attached to whichever carbon atom at positions 2 and 4 is not part of said double bond, R is halogen, alkoxy (C.sub.1-6), phenoxy, hydrocarbyl (C.sub.1-18), halohydrocarbyl (C.sub.1-18), m = 0-3; n = 0, 1; R.sub.1 is hydrogen or methyl; and R.sub.2 is hydrocarbyl free from substituents reactive with isocyanate.