2,907,745 United States Patent Office Patented Oct. 6, 1959

2 structural strength and, therefore, useful in load-bearing ...... 2,907,745. applications. POEYURETHANE OF A POLYISOCYANATE, AN Fhese and other objects are accomplished by the present - ACTIVE HYDROGEN COMPOUND, ANEDA HY invention which contemplates the reaction of a substantial DROXYARYL, ALEPHATIC ACID 5 amount of an isocyanate or isothiocyanate, at least half of which must contain two or more isocyanate or isothio Sylvan O. Greenlee, Racine, Wis, assignor to cyanate groups per molecule, with an aliphatic acid, hav S. C. Johnson & Son, Inc., Racine, Wis. ing a total of at least five carbon atoms with a single No. Drawing. Application January 16, 1957 carbon atom being substituted with two hydroxyaryl 0. groups; and an organic compound having an active hy Seria No. 634,411 drogen groups at least two of the following radicals: 7 Claims. (C. 260-47) YH, CYYH, NH, and CYNH, where Y is oxygen or sulfur, which compound is free of other reactive groups. This invention relates to novel resinous compositions It has been found that the addition of hydroxyaryl of matter of the polyurethane type and is directed more 5 aliphatic acids to a polyisocyanate-active hydrogen com particularly to synthetic resinous compositions derived pound reaction mixture is: an unusually advantageous from the reaction of hydroxyaryl aliphatic acids with measure for obtaining polymeric resinous compositions polyisocyanates in presence of an organic compound characterized by excellent protective coating and adhesive capable of entering into the reaction and exerting an in properties when used as a film, and high structural strength fluence upon the nature of the resulting product. 20 when cast into foam resin bodies. The hydroxyaryl It is known a urethane resin may be obtained by re aliphatic acids are especially adapted for the reaction by acting a polyisocyanate or polyisothiocyanate with a virtue not only of the presence in each molecule thereof group of compounds characterized by one or more of of a plurality of functional groups reactive with both what has been termed "an active hydrogen group.” Fore the: isocyanates and active hydrogen compounds, but be most among the "active hydrogen' compounds, at least 25 cause of the novel combination of hydroxyl and carboxyl as regards commercial development, have been the poly radicals. that make up this plurality of groups. As will ester, compounds, although polyhydroxy-, polyamino-, i. be explained more fully, both hydroxyl and carboxyl radicals condense with an isocyanate:group and, thus, are polyamido-, and polythio-compounds are also recognized of value in forming a resinous product; in addition, the as being more or less useful in this connection. The 30 carboxyl radical during the course of the condensation resinous products. derived from this reaction are depen decomposes to liberate carbon dioxide which can be made dent for their characteristics, for the most part, upon the use of in producing foam resin-structures. Hydroxyaryl cyanate:structure acting of the principally active: hydrogen as a physicalcompound coupling with the agent iso aliphatic acids are high: melting, cyclic compositions of between residues of the polyester or other compound. unique symmetrical structure and tend to contribute to The range or variety of properties. has thus been limited 35 the reaction product such properties as outstanding chemi by the types of structures possessed by available active cal resistance and superior hardness and toughness. hydrogen compounds, and the formulator has often Chemical resistance is, for example, of great value in the found it quite difficult to develop products having the formulation of protective coatings which are likely to be desired characteristics: subjected in the course of ordinary usage to contact with The primary object of the present invention is the 40 various chemicals. The presence in the resin of residues incorporation in a polyurethane-forming mixture of a having a symmetrical structure results in a more rigid compound having multiple functionality both with respect product, a feature of much advantage in polyurethane to: isocyanates and isothiocyanates and active hydrogen foams. compounds, by means of which compound a broad The hydroxyaryl aliphatic acids contemplated for re spectrum of polymers of this type can be obtained. 45 action according to this invention may be, and preferably Another of the objects of this invention is to provide are, prepared by condensing a phenolic compound with a new class of synthetic resinous compositions which are a keto-acid under such conditions that two hydroxyaryl capable of further reaction to give infusible, insoluble radicals are attached to the same carbon atom of the acid. materials suitable for use as protective coatings, adhesives, In order for the yields of this reaction to achieve useful and molding resins having a variety of properties. 50 levels, it is necessary, first, that the keto-carbon atom A further object is the synthesis along the general lines occur at the position adjacent a terminal methyl group, of established urethane reactions of a film-forming prod and, second, that the keto-acid has at least five carbons in uct characterized, by virtue of the novel reactants from the aliphatic chain. The keto-acid of this type which which it is derived, with improved properties, especially 55 has only four carbon atoms, aceto-, is highly as regards resistance to attach by chemicals, resistance to unstable under the conditions necessary for the reaction wear, and resistance to penetration and solvent action by and is unsatisfactory. The five-carbon acid, levulinic Water. . acid, gives excellent yields. Higher acids are apparently By suitable: adjustment of the conditions of the reaction useful, but these exist principally as laboratory curiosities and the ingredients, the product of the invention may be 60 and are not available in commercial quantities. There caused to assume a cellular or foam state, and, accord is disclosed in prior co-pending applications, Serial Nos. ingly, an additional aim of the invention is the provision 464,607 and 489,300, filed October 25, 1954, and of lightweight three-dimensional solids possessing good February 18, 1955, respectively, a number of illustrative 2,907,745 3 4. acids that have been found to be particularly suitable for While, as has already been mentioned, urethane re use, as well as methods of preparing the same. These action requires a polyisocyanate compound, it is desirable acids consist of the condensation products of levulinic for certain applications to alter the product by using, in acid and , substituted , or mixtures of addition, a minor portion of a monoisocyanate. Many of phenol and substituted phenols and shall, for the sake the reaction products of Diphenolic Acid with polyiso of brevity, be referred to herein as “the Diphenolic Acid.” cyanates tend to be brittle infusible products; on the other The term "substituted phenols' is used herein to hand, this tendency may be counteracted by the addition embrace phenols and phenolic compounds wherein one to the reaction mixture of a proper amount and type of or more hydrogen atoms of the phenyl nucleus is re monoisocyanate, particularly when combined with the placed by an atom or group that does not enter into, or O proper amount and type of active hydrogen compound. otherwise interfere with, the condensation of the com xamples of Suitable monoisocyanates are octadecyliso pound with the keto-acid. Thus, for example, the nu cyanate, hexyl isocyanate, and decylisocyanate, to men cleus may be alkylated with a methyl or other alkyl group, tion just a few of the simpler compounds. Long-chain preferably having not more than five carbon atoms, as monoisocyanates, i.e. having more than 11 carbon atoms, disclosed in the aforementioned application, Serial No. 5 are more effective as regards flexibility. Unsaturated com 489,300, or halogenated with bromine, fluorine, chlorine, pounds can also be utilized and provide an additional or combinations thereof, provided that a total number of curing or converting aid. The amount of the mono substituents, including hydroxyl groups does not exceed compound that is added to the reaction mixture will vary three. The Diphenolic Acid derived from substituted depending upon the characteristics desired in the product. phenols, such as the alkylated phenols, is sometimes 20 As a general rule, there should be present a greater more desirable than the products obtained from unsubsti amount of the poly-compound that the mono-compound, tuted phenols since the alkyl groups tend to provide better which is to say, that the monoisocyanate should be less organic solvent solubility, flexibility, and water-resistance, than 50% of the total of all isocyanates in the reaction as well as influencing the nature and extent of subsequent 1mixture. If a more rigid, brittle material is sought, the reactions for which the acids are adapted. However, the 25 quantity of the mono-form should be decreased, while, unsubstituted product is usually more readily purified. if more flexibility is the desideratum, it should be in The second component necessary for the reaction of the creased toward the upper limit just mentioned. The func present invention is an isocyanate or isothiocyanate com tional group of the mono-form may react with the car pound. In order that a resinous product be obtained, the boxyl or phenolic hydroxyl groups of the acid to reduce isocyanate or isothiocyanate compound must contain two 30 cross-linking within the polymer chain and thereby en or more isocyanate or isothiocyanate groups, a plurality hance the softness and pliability of the polymer in pro of functions being essential if a chain or cross-linked portion to the amount present, or a functional group of structure is to be developed by condensation with the each of two molecules of the monoisocyanate may react functional groups of the Diphenolic Acid and/or the with two of the functional groups of a single molecule active hydrogen compound. Accordingly, the isocyanate 35 of acid and, thus, terminate the chain. Reaction of the may be defined as a compound having the general formula mono-compound and the active hydrogen compound is R(NCX), where X is a chalcogen having an atomic also a possibility, which reaction may also end the growth weight less than 33, i.e., oxygen or sulfur; z is an integer of the polymer molecule or reduce cross-linking. of more than one; and R is a polyvalent organic radical The active hydrogen compound is the final component with the number of valences being equal to z. There 40 of the reaction mixture described herein. For the purpose are numerous compounds coming within this formula of the invention, the active hydrogen compound must in that are suitable for the reaction and no attempt will be clude at least two of the radicals -OH, -COOH, made to give an exhaustive list. The following are con fy-CONH2, the discussion, -NH2-SH,-COSH,-CSNH. compounds meeting this requirementTo simpli sidered illustrative and will suggest to the expert a variety have been grouped into the following classes: (A) the of others: alkylene diisocyanates; such as ethylene di polyhydroxy compounds, (B) the polybasic acids, (C) isocyanate, trimethylene diisocyanate, tetramethylene di the polyamines and polyamides, (D) miscellaneous an isocyanate, hexamethylene diisocyanate, decamethylene alogous Sulfur compounds, and (E) the polyester resins. diisocyanate, and their corresponding sulfur analogues; As will be seen later, compounds containing more than cyclo-alkylene diisocyanate, such as cyclopentylene diiso one type of radical, i.e., "hybrid” compounds, have not cyanate, cyclohexylene diisocyanate, and their correspond 50 been classified independently but are included in these ing sulfur analogues; aromatic diisocyanates, such as m five groups. In this case, as a rule, the compound is classi phenylene diisocyanate, naphthalene diisocyanate, di fied in that group of the several into which it might fall by phenyl-4,4'-diisocyanate, and their corresponding sulfur virtue of the radicals it contains, which has the highest analogues; aliphatic-aromatic diisocyanates, such as numerical designation in accordance with the above -1,4-diisocyanate, diphenylene methane diisocyanate 55 break-down. For example, a compound containing both and their corresponding sulfur analogues; hetero-diiso hydroxy and amine radicals appears with the sulfur com and disothiocyanates, such as pounds, and a compound having recurring ester linkages SCNCHOCHNCS and free carboxyl radicals appears with the polyesters. 60 The first of these classes are the polyhydroxy com and SCNCH2SCH2NCS; and isocyanates and isothio pounds, which, as contemplated herein, embraces the cyanates having more than two isocyanate or isothio aliphatic, alicyclic, heterocyclic, and aromatic compounds cyanate groups, such as 1,2,4-triisocyanate, 1,2,2- containing at least two hydroxy radicals. Examples of triisocyanatobutane, and toluene trisocyanate. From these compounds are the alkylene glycols, such as ethylene among these and other polyisocyanates and polyisothio glycol; polyalkylene glycols, such as diethylene glycol and cyanates, the following are preferred largely by reason of 65 the CarboWax” series manufactured and sold by the their ready commercial availability; toluene 2,4-diiso Carbide and Carbon Chemical Company; glycerol, Cyanate, toluene 2,6-diisocyanate, methylene bis(4-phenyl erythritols, higher alcohols, such as mannitol and sorbitol; isocyanate), 3,3' bitolylene 4,4' diisocyanate, and hexa aromatic alcohols, such as resorcinol, hydroquinone, and methylene diisocyanate. In order to simplify the re bis-phenol; and resinous alcohols, such as the epoxides. mainder of the discussion, the repetitious recital of 70 Mixtures of the Diphenolic Acid with dihydric phenols, both the oxygen and sulfur forms will be dispensed with; particularly the alkylidene diphenols, in reaction with the only the oxygen compound will be given but will be isocyanates give rigid, infusible products possessing ex understood as embracing the corresponding sulfur cellent chemical resistance to alkali and water when analogue. 75 formed as films and outstanding rigidity when cast as

2,907,745 5 ...... foam resin structures. It is well known that the poly "Thiokol" and prepared by reacting an alkaline polysul hydric alcohols, such as the long-chain glycols, given on fide with an organic dihalide, trihalide, or mixtures of . reaction with the isocyanates soft flexible-type composi the two. These polymers are thought to have thiol ter tions of relatively low chemical resistance. Modification minal groups. Preferably, the liquid polymers are em of these compositions with Diphenolic Acid has been 5 ployed because of their relatively low molecular weight, found to greatly increase the chemical resistance of pro ease in handling, and ease in admixing with other re tective coating films prepared therefrom as well as to actants. As is well known, these materials undergo re strikingly heighten the rigidity of foam resin structures action with various coupling agents, or can be cured with produced therefrom...... numerous curing agents to form rubbery polymers which Next in the classification are the polybasic acids. Ex 0. are usually soft and flexible. When compounded with a amples of these acids are the saturated aliphatic-polycar Diphenolic Acid and an isocyanate, thioresins yield boxylic acids such as adipic and tricarboxylic acid, azelaic smooth, tough, flexible products having much augmented acid; unsaturated aliphatic-polycarboxylic acids, such as chemical resistance. Other sulfur compounds, such as the fumaric acid and aconitic acid, and aromatic polybasic simple mercapto acids and mono- and di-mercaptans, may acids, such as the isomers of benzene dicarboxylic acid. Polyfunctional acids are of particular interest in connec 5 be used in conjunction with Diphenolic Acid in the for tion with the formation of resin foams as the carboxyl objects.mulation of valuable coating, adhesive, and molded group decomposes upon reaction with an isocyanate to Finally, there are the polyester resins, which are poly release carbon dioxide. With the addition of a Diphenolic mers, having recurring ester linkages and unreacted hy Acid, further-carbon dioxide is available from the car 20 droxyl and carboxyl terminal groups formed by reacting boxyl group of the Diphenolic Acid and enhanced foam a polybasic acid with a polyhydric alcohol. The nature ing results. This is advantageous since enhanced foam of the reactive groups is determined by the proportion ing was usually previously obtained by adding substan of the reactants. Thus, an excess of the alcohol favors tial amounts of water. As is well known, water reacts terminal hydroxyl groups while an excess of acid favors with an isocyanate to yield carbon dioxide and a carba 25 terminal carboxyl groups. By properly balancing the mide. Consequently, extensive foaming by the prior art amounts of each, terminal groups of both kinds can be method required an excess of isocyanate, a relatively ex procured. There are a number of polyester compounds pensive material, adding on a weight basis to the cost of available commercially, one example being a series having the product and the reaction was difficult to control. In hydroxyl values within the range of 70-1000 and acid addition, the Diphenolic Acid serves to strengthen the 30 numbers within the range of 0-80 sold under the trade rigidity of the foam and causes the cell arrangement to name "Multron” by the Mobay Chemical Company. be disconnected or closed rather than open. Where the Among the polybasic acids that can be used are succinic, combination of isocyanate, polybasic acid and Diphenolic adipic, maleic, sebacic, azelaic, fumaric, and dimerized Acid is used as a film or coating, the Diphenolic Acid acids, such as dimerized vegetable oil acids prepared and tends to balance the essentially soft influence of the poly soid by Emery Industries, Inc. Suitable polyhydric alco basic acid, permitting the formulation of tougher, harder hols include ethylene glycol, diethylene glycol, triethylene films than would otherwise be the case. One interesting glycol, pentaerythritol, dipentaerythritol, tripentaerythri property of the polybasic acids in this association is their tol, Sorbitol, mannitol, glycerine, trimethanol propane and tendency to improve the characteristics of the film in triethanol propane. - - - the presence of water, presumably due to the hydrophilic 40 It is well known that reaction of polyester resins with character of such acids. Films which are highly hydro the polyisocyanates results in soft flexible foam resin phobic, are whitened by prolonged contact with water. structures and soft coating compositions and molding ma By adding material having hydrophilic properties to the terials. The use of Diphenolic Acid in conjunction with film-forming mixture, the hydrophobic. character of the these polyesters and isocyanates has been found to be an film can be reduced to a level at which whitening does 45 excellent mode of promoting rigidity in foam resin struc not occur without undue loss of overall resistance to tures of this type. Thus, moderately to completely stiff Water. three-dimensional articles can be easily obtained merely The third class, the polyamines and polyamides, is char by incorporation of the acid in selectively increased acterized by the presence of an -NH2 radical, which in amounts. Variation in density of the solid product may the case of the polyamides is combined with a carbonyl 50 also be effected by this means. In the field of protective group as the radical.--CONH2. Examples of this class coatings and adhesives, an analogous hardening and are the alkylene and polyalkylene diamines, such as toughening influence by the EDiphenolic Acid exists so ethylene diamine, and hexamethylene diamine; hetero that products of this kind display substantially enhanced cyclic polyamines, such as diethylene diamine; and aro resistance to chemical attack and deterioration as well matic polyamines, such as phenylene diamine; the ali 55 phatic diamides, such as malonamide, succinamide and as general wear and tear without necessarily involving adipamide; aromatic diamides, such as phthaldiamide; and undue sacrifice of the natural flexibility and clarity of the resinous polyamides. Compounds containing annino the polyester resins. groups are of particular value in accelerating the reaction. The general chemistry of the present reaction is basi It is interesting to observe that polyamines are slightly. 60 cally simple. It is well known that isocyanates react more inclined to impart flexibility to products than the with the various chemical functional groups of the com polyamides. Thus, a product of balanced flexibility pounds employed herein and these reactions may be ill rigidity, or increased rigidity, may be obtained by the lustrated as follows: addition of a Diphenolic Acid. The poly-nitrogen com pounds are also useful where products having high chemi (1): Hydroxyl group: cal and water resistance are sought. ROH--R'NCO->R'NHCOOR Another class of active hydrogen compounds is the (2). Carboxyl group: sulfur-containing chemicals. As a general rule, this class RCOOH--R'NCO->R'NHCOOCOR-R'NHCOR--CO, embraces the corresponding sulfur analogues of the mem (3) Primary amino. group: bers of the other classes. 70 RNH--RNCO->R'NHCONHR ethanedithiol and propane-trithiol,Thus, polythioacids,polythiols, such poly as (4) Amido group: thioamides, and resinous polythio-compounds are in RCONH--R'NCO->RNHCONHCOR cluded, among others. The most useful of these com The same reactions take place where sulfur is substituted pounds are the thioresins sold under the trade name 75 for any oxygen in these reactants, 2,907,745 -7 8 - : In the present invention, it is postulated that the re reacted with functional groups of the polyisocyanate, action occurs within a system of three or more compo For this reason, a preferred range is 2:1 to 1:2 of acid nents, each of which is characterized by at least double and active compound to isocyanate on an equivalent basis functionality. Accordingly, while the union of any two with a 1:1 ratio being most desired. : , groups will proceed as set forth above, it will be appre If a monoisocyanate is employed along with the poly ciated that the resultant product will in any case be isocyanate, the number of reactive foci of the Diphenolic polymeric. Further, it will be apparent that the possible Acid and active hydrogen compound available to the arrangements that may be taken within the polymer functional groups of the polyisocyanate is lessened. In molecule by the residues of the reactants are entirely arriving at the amounts of reactants to be utilized, the too numerous to be presented herein. Due to the high 10 mono-compound must therefore be considered, and in reactivity of isocyanate groups, one would expect the Such case the equivalent weight of the isocyanate is the condensation between these groups and the functional groups of the Diphenolic Acid to take precedence over total of the equivalent weights of the mono- and poly any possible reaction between the acid and the active hy compounds. drogen compound. Thus, it can be predicted that the 5 In general, the procedure by which protective coating polymer molecule comprises Diphenolic Acid residues films are prepared in accordance with the present inven linked together by isocyanate residues alone or which tion involves merely adding at ordinary temperatures the are themselves coupled by means of the residues of the Diphenolic Acid and active compound to the isocyanate, active hydrogen compound. Where the isocyanate and forming a film of the desired thickness of the mixture, active hydrogen compound are difunctional, the acid 20 and converting the mixture by exposure either to air at residues would be separated by essentially linear chains normal temperature or to heat. In some cases, it is de with cross-linking taking place between the residues in sirable to dilute some or all of the reactants, e.g., in or adjacent chains due to the three reactive groups of the der to lower the viscosity of the mixture and, thus, vary. Diphenolic Acid. With isocyanates and/or active hy the film thickness of a single coat, and/or in order to drogen compounds having more than two functions, cross 25 dissolve the Diphenolic Acid at room temperature. Any linking to a much greater degree would ensue. solvent that is inert to both the acid and isocyanate may The diversity of the isocyanates and active hydrogen be used, an example being methyl ethyl ketone among compounds that can be employed makes it virtually im many others. The mixture of reactants, either diluted possible to prescribe a fixed set of rules governing the 30 or not, has been found to be reasonably stable provided choice of a class of compounds, the particular member it is not heated or exposed to air for excessive periods. of that class, as well as the amounts of the member. Some of the classes and the 12 individual members are Such Stability is a feature of considerable importance as more or less equally suited for use in producing a given it permits large quantities of the mixture to be made up product so that a choice depends in many instances upon at one time and then used as needed. For heat cure, the personal preference of the formulator, such prefer 35 temperatures of about 80-175 C. for times of about one ence being based, for example, on his greater experience hour to about five minutes have been found satisfactory. in working with certain types of materials than with oth For a room temperature cure, it is preferred that ers. As a rule, aliphathic compounds favor flexibility and any of the well known conversion catalysts for reactions softness with the extent of these properties increasing 40 of this type, such as triethanolamine, be added in small with the chain length. Conversely, compounds having a amounts in order to reduce the amount of time needed tightly knit or cyclic molecular structure favor rigidity for the film to harden. When early conversion is of no and hardness. As a consequence, a wide range of prop Special advantage, the catalyst may be dispensed with. erties can be developed by the careful selection of re As the examples show, the characteristics of the cured actants: that is, all may promote flexibility, they all 45 films vary with the particular combination of reactant may promote rigidity, or some one and some the other and amounts that are employed, with some being better in order to cover the gamut, between the two extremes. than others, as would ordinarily be expected. As a Along with the specific reactants, the properties of the whole, however, the films possess characteristics that product are also influenced by the amount of each re compare favorably with many other available materials actant that is employed. Because of the high reactivity 50 So that the product of the invention is quite useful for a of the isocyanate, for the purpose of defining propor variety of purposes. For example, in numerous in tions it may be considered that the Diphenolic Acid and stances, the films of this invention have withstood boil active hydrogen-containing compound react as a "unit” ing Water for 16 hours and a 5% caustic solution with the isocyanate. Within this suppositious “unit,” the 55 for more than 90 hours without any indication of failure. active compound may constitute from about 5 to about Where Solid foam or cellular structures are desired, 65% of the whole, determined on the basis of equiva they may be obtained by mixing the concentrated Di lent weight, with the acid making up the rest. Below phenolic Acid and active hydrogen compound with a 5%, the effects of the active compound are rarely signifi suitable conversion catalyst, of which triethanolamine is cant, while above 65%, the contribution of the acid is 60 again an example, in an appropriate reaction vessel at counteracted excessively or is not sufficiently great to be temperatures at or above the melting point of the acid, of real value. Experience has indicated that the Di adding the isocyanate while agitating, pouring the mix phenolic Acid and active hydrogen compound, consid ture into a mold, allowing the mixture to foam unim ered together, may be reacted in amounts, again calcu peded, and converting by heating, as in a draft oven, at lated on an equivalent basis, varying from about one a temperature of about 80-175° C. or more for from fifth of the isocyanate up to about five times the isocy about 5-30 minutes, or by normal temperatures for much anate. Some products prepared from amounts outside longer periods of time. Although not essential, it is this range may display useful characteristics attributabie usually desirable to employ an emulsifier in order to ob to all three of the reactants, but this appears to be the tain a more homogeneous mixture of the reactants. The exception rather than the rule, and, for the most part, 70 reaction usually proceeds instantaneously at or above the valuable products fall within this range. From a con melting point of the acid. The instant process may be sideration of the reaction, it will be appreciated that the carried out readily in any system which provides for optimum situation prevails where all of the functional stirring and has sufficient space for the foaming action groups of the acid and active hydrogen compound are 75 to proceed unhindered. A modification of a unit cur 2,907,745 fently used in commercial urethane foam production 10 may be employed. Such a system comprises two supply TABLE I-REPRESENTATIVE DIPHENOLIC ACID tanks connected to a pressure-mixing nozzle by suitable feed lines. One tank contains the isocyanate and the Isocya Abbre ... nate. other tank contains the Diphenolic Acid and active com No. Acid viation equiva pound emulsified with the emulsifying agent and catalyst. lent (ob As pure or substantially pure Diphenolic Acid is solid served) at room temperatures the latter tank must be heated. 1. Condensation products of lewulinic acid and phenol: A mixture consisting of 376 parts DPA 89.7 The acid and isocyanate are fed from the tanks to the of phenol, 16 parts of , and nozzle where they are mixed under pressure and flowed 10 250 parts of 37% aqueous was agitated at 48-52° C. for 66 hours. into pans where the foaming reaction is allowed to The upper organic layer was removed from the aqueous EICl for decantation. proceed unhindered. Again, the foams may be cured The product was then purified by vacuum in a suitable draft oven at elevated temperatures, thus distillation of the volatile unreacted ma terials by heating to 180° C. at 32 mm. accelerating the operation. Although the foams may be. pressure. The residual product amounted cured at ordinary temperatures as in the case of the films, 15 to 247 parts (86.5% of theoretical) having a softening point of 80 C. and an acidinum this considerably prolongs the curing time and a heat cure ber of 155. Purification of this product by is preferred. first dissolving in aqueous bicarbonate. As has already been briefly mentioned, the Diphenolic solution,acid, followed reprecipitating by recrystallization with mineral from hot water gives a white crystalline coin Acid as well as carboxyl-containing active compounds pound melting at 171-172°C., having an 20 acid value of 196. , are especially well suited for the formation of urethane 2. Condensation product of levulinic acid and foams by reason of the carboxyl group or groups which meta-cresol: A mixture of 378 parts (3.5 DCA. 198 mois) of meta-cresol, 16 parts (1 mol) of they contain. These groups in the course of the reaction levulinic acid, and 250 parts of 37% aque: decompose to form gaseous carbon dioxide which bub ous hydrochloric acid was agitated at 50: C. for 72-hours. The upper organic layer bles through the mixture to produce a cellular structure. 25 was removed from the aqueous HCl by Thus, a foaming medium is inherently present, eliminat decantation. The product was then puri fied by vacuum distillation of the volatile ing the need, in many instances, of an external foaming unreacted materials by heating to 170. C. agent, this being especially true where a polybasic acid at 30 mm. pressure. The residual product constitutes the active compound. With other active thehas anpure acid Diphenolicnumber of 166Acid=1.78). (theoretical The for 30 yield amounted to 184 parts (58.6% of compounds the use of external foaming agents, such as theoretical). .. Condensation of levulinic acid and a mixture water, to assist in the foaming action may not be pre 3--- of phenol and ortho-creSol: Similar treat DPCA. 235 cluded entirely as it sometimes proves advantageous to ment of a mixture of 3.5mols of a technical add small amounts of water, say up to about 5% by cresol containing 40 parts phenol and 60 andparts 250 ortho-cresol, parts of 37% 1 hydrochloric mol of levulinic acid acid,gave weight of the mixture. The use of water merely as an 35 275 parts (90.5% of theoretical) of a product assistant does not add unduly to the curing time of one having and acid number of 149. 4.- Condensation of levulinic acid and Xylenol: hour or less which is in distinst contrast to typical present Similar treatment of a mixture of 3.5 mols DXA-. 168 of technical xylenol, a cresylic acid, Sup commercial polyurethane foam processes, wherein water plied by the Koppers Company, Inc., is relied upon as the sole or principal foaming agent, under the trade name X-2, which contains 95% xylenols of which about 30% is 3,5- which require a post-cure of some 24 hours duration. 40 xylenol and has a distillation range at the The density of the foams made as described herein varies 5% point of 214-217 C. and at the 95% not only with the particular isocyanate selected for re andpoint 250 of 220-225°C.;parts of 37% 1 mollevulinichydrochloric acid;acid reacted at 50° C. for 96 hours gave a prod action but with the temperature of the conversion as well. uct having an acid number of 166 in yields It has been found that as the temperature of this stage of around 50% of the theorctical amount. is increased, the density of the foam also increases, due 45 presumably to the increased loss of CO2 from the mix in selecting actual amounts of the acid that should be ture at the higher temperatures. used. The method used in determining the observed The toughness and rigidity contributed by the Di values as listed involves reacting a sample of the acid phenolic Acid are especially significant in the case of 50 with an excess of toluene-2,4-diisocyanate and then deter foam structures made in the past from isocyanate and mining the excess isocyanate by reaction with di-n-butyl active hydrogen compound reaction products which have, amine. Specifically, the technique used is as follows: for the most part, been of rather soft, spongy texture. To 25 ml. of methyl isobutylketone is added 3 grams of The toughness and rigidity together with the resistance. toluene-2,4-diisocyanate previously standardized against 55 di-n-butylamine and a weight of the acid such that the to water and common chemicals that the present foams diisocyanate is present in approximately 100% excess. exhibit as well as a very low density when compounded To this mixture is added triethylamine in an amount to this end, constitute a rather exceptional combination. equal to 1% of the weight of isocyanate and the acid. in this field, so that the present invention should be par The mixture is refluxed for a period of one hour. After ticularly valuable in producing foam structures for such 60 cooling to room temperature, the condenser, walls are uses as air domes, insulation, crash linings for vehicles, rinsed with about 25 ml. of redistilled toluene. To this aircraft, etc., and structural components alone or in mixture is added 25 ml. of 2 N di-n-butylamine. This conjunction with outer coverings of wood or metal. mixture is warmed to the boiling point, allowed to stand For the sake of brevity as well as convenience, most for one hour at which point 75 ml. of methanol is added, of the remainder of this disclosure will be presented in and the excess di-n-butylamine back-titrated with 1 N the form of four tables, the first three giving examples 65 alcoholic hydrochloric acid. of the three reaction components, along with some perti The acid number given for each acid has its usual nent information concerning them, and the fourth pro meaning, which is the number of milligrams of potassium viding Working examples of the invention in the coating hydroxide necessary to neutralize the acid content of field. one gram of the sample, and provides an indication of It will be observed that an isocyanate equivalent is the degree of acidity of the product. Specified for each acid. The isocyanate equivalent is It will be noted that an observed and theoretical amine defined as the weight of the acid which will react with - equivalent is specified for each isocyanate. The amine one equivalent of the isocyanate and will be of assistance equivalent refers to the weight of the isocyanate con 5. taining one isocyanate group and reacting with one mole. 2,907,745 - 11. 2 TABLE II.-REPRESENTATIVE ISOCYANATES Amine equivalent No. Commercial source, trade name, and abbreviation Structure -----m- - Observed Theory

CE . . . . l----- E. I. du Pont de Nemours & Co., Inc.; Hylene T.; NCO 90.62 87. 07 Hy T.

NCO Toluene-2,4-diisocyanate H 2----- E.E. duPont de Nemours & Co., Inc.; Tylene MI; ocN-( )--( )-Noo 139, 98 25.2 Hy M. -- N Methylene bis(4-phenyl isocyanate) Me Me 3----- National Aniline Div.; Nacconate 200; N 200------O ON-(D-g >-NC O 32.78 132.13 3,3'-bitolylene-4,4'-diisocyanate NCO

4----- Mobay Chemical Co.; Mondur N5; MON5.------I6, 58 105.09

OCN Naphthylene-1,5-diisocyanate CH

--NCO

5- - - Mobay Chemical Co.; Mondur TM; MOTM-----. CH,-(, d–H 107.78 23.45 N6O - -, -NCO

CH Triphenylmethane triisocyanate 6..... Mobay Chemical Co.; Mondur HX, MO HX------: OCN (CH)aNCO 103.39 84.01 Hexemethylene diisocyanate 7. --- Mobay Chemical Co.; Mondur O, MOO------CEI3(CH2)NCO 342.32 295.0 Octadecylisocyanate GB, CH 8----- Shell Development Co.; Durenediisocyanate; Dur. OCN- NCO 111.22 108,12 CH, CH, 2,3,5,6-tetramethyl-1,4-benzene diisocyanate of di-n-butylamine. Since the isocyanates available com into a warmed glass bulb and the neck sealed off in a mercially are not necessarily chemically pure, the ob flame. Sample weight is determined by the difference served values were obtained for use as a guide in formu 65 in weight between the empty and the filled bulb. The lating reaction products therefrom as these values pro bulb was immersed in the Erlenmeyer flask and crushed vide a measure of the actual purity of each compound. beneath the surface of the liquid. The solution was The analytical procedure used to determine amine. heated to boiling and allowed to cool 1 hour. 100 ml. of equivalents of diisocyanates is found in Monsanto Chem technical methanol and 0.5 ml. of bromophenol blue in ical Company's Technical Bulletin #P-125 and is gen 70 dicator was added. It was then titrated with 1 NHCl to erally as follows: a yellow end point. The indicator was prepared by Twenty-five milliliters of redistilled toluene and 25 ml. taking 0.1 g. of bromophenol blue, 1.5 mi. of 0.1. N of approximately 2 N di-n-butylamine were placed in a NaOH diluted with 100 ml. of distilled HO. The aver carefully cleaned and dried 250 ml. or 500 ml. Erlen age precision demonstrated by these determinations was meyer flask. ... The sample of diisocyanate was drawn 75 1.29%. - 3,90,745 13 14 TABLE III-ACTIVE HYDROGEN. COMPOUNDS A. POLYHYDROXY COMPOUNDS

Compound Abbrev.used in Isocyanate equivalent Observed Theoretical Ethylene glycol------27.64 3.03 1,4-butanediol---- 39.26 45.06 Diethylene glycol 44; 76. 56 Polyethylene glycol 400------...... ------163.48 90-20 (Carbidestokes at & 210 Carbon F.) Chemicals Co., described as having M.W. 380-420; viscosity 7.3 centi (CarbidePolyethylene & Carbon glycol 1000------Chemicals. Co., M.W. 950-1050; viscosity 17.4 centistokes at 210°F.) PG-1000; .409,76 500 CarbidePolyethylene & Carbon glycol Chemicals 4000------Co., M.W. 3000–3700; viscosity 75-78 centistokes at 210°F.) PG4000.- . 1,651.9 1,500-1,850 (CarbidePolyethylene & Carbon glycol Chemicals 6000------. Co., M.W. 6000-7500; viscosity 700-900 centistokes at 210°F) PG-6000-3,475.6 3,000-3, 750 Glycerol (C.P. grade).------. G------29,53 30.6 ". . Pentaerythritol...... PN.------24, 24. 34,04 (ShellEpon 864'------Chemical Corp. An epoxy resin prepared from the condensation of epichlorohydrin Epon 864. 311.63------with bis(4-hydroxyphenyl)-dimethyl methane in the presence of alkali having a melting 1929)oint (Durrans'of 40-45°. C.Mercury epoxide Method, equivalent Journal 300-375.) of Oil & Colour Chemists' Assoc. 12, 173-175. (ShellEpon 1007'------Chemical Corp. An epoxy resin prepared from the condensation of epichlorohydrin Epon 1007. 360.29 with bis(4-hydroxyphenyl)-dimethyl methane in the presence of alkali having a melting point (Durrans' Mercury. Method) of 127-133°C.; epoxide equivalent 1,550-2,000.) (InBis(4-hydroxyphenyl)-dimethylmethane-formaldehyde a 3 liter, 3-neck flask provided with a mechanical agitator, condensate------. a thermometer, and a reflux BioF------98.78 ------condenser was placed 912 parts of bis(4-hydroxyphenyl)-dimethyl methane, 960 parts of 37% aqueous formaldehyde and 2.3 parts oxalic acid. With continuousagitation the reaction mixture was heated to reflux temperature and refluxing continued for ihr. After permit ting the reaction mixture to cool to around 50°C. the water layer was removed by decan- ; tation. The phenol-formaldehyde layer was then washed 3 times with water which in each case was removed by decantation. The last portion of water was removed by dis tillation at reduced pressure using a water aspirator system which gave pressure around 30-40mm. The flask temp. during the removal of this last portion of water ranged from The70-90° nonvolatile C. The product, content wasamounting SE5 to 1,065 parts, was a clear,, heavy, syrupy material. p-t-Butylphenol-formaldehyde(The procedure of preparation, condensate------including the dehydration step, ------was the same as that used BPF 156.54 ------with bis(4-hydroxyphenyl)-dimethyl methane above. A mixture of 1,000 parts of para tertiary butylphenol, 1,067 parts of 37% aqueous formaldehyde, and 10 parts of sodium product.hydroxide Thewas usednonvolatile to give content a final yieldwas 93.6%) of 1470 parts of a clear, almost colorless syrupy Hydroquinone,Res9rcinol------C. P------105.38161:44 55.05 l,5-dihydroxynaphthalene.---- 217.38 80.08 4,4'-dihydroxybenzophenone------22.0 107.1

Bis(4-hydroxyphenyl)-dimethylmethane------. 304, 22 4.0

B. POLYBASIO ACIDS

87.53 94. 7135 73.07 57.28 58.03 52.36 58.03. 16602 67.04 485.29 83.06 C. POLYAMINES AND POLYAMDES Hexamethylenediamine. 31.96 29,05 Diethylenetriamine- 17.99 20.63 Triethylene tetraamin 27.50 26,38 Phenylene diamine 41.54 27.03 Diethanolamine- 41.2 35.05 Adipamide------106.22 38.04. Phthalamide------140.36 4.04 Malonamide------63.65 25.52 es. p-Toluenesulfonamide. 98.63 85.60 Polyamide resin------380.03 312.03 (In a 3-liter, 3-neck flash provided with mecha. agitator, thermometer, and water trap with a refix condensef above was placed 1,545 parts of Emery Industries, Inc., TDimer Acid #955 (a dimerized soya bean oil acid) and 269 parts of ethylenediamine. The flask was provided with an inlet for an inert gas. With continuous agitation and in an inert atmosphere of nitrogen gas the reaction mixture was heated from 94-220°C. over a period of 12hours. 165 parts of water were removed from the reaction mixture during this period. The resulting polyamide resin had an acid number of 3.2, and a softening point of 87-89° C. (Durrans' Mercury Method).) - - - - - D. SULFUR-CONTAINING COMPOUNDS

2-mercaptoethanol.------Thiokol Liquid Polymer LP ((Thiokol Chemical Corp.) Described as ling having WiscosityHS-(CHO at 25° C.CH-O-CHS-S)-CH-O-CH-O-CH-SH of 700-1,200 centipoises.) Thiokol((Thiokol Liquid Chemical Polymer Corp.) LP-8------Described as having formula LP8.------380.68 ------having viscosity at 27°C. of 250-350 centipoises.) Thiokol((Thiokol Liquid Chemical Polymer Corp.). LP33.------Described as having formula LP33.------597.66 ------having viscosityHS(CH-O--CH-O-CHS-S)6-CH-O-CH-O-CH-SH at 25°C. at i300-1,550 centipoises.)

2,615,008,1 Preparation 2,688,805, of 2,688,807, these epoxide and 2,698,315. materials as well as illustrative examples are described in U.S. Patents 2,456,408, 2,503,726, 2,615,007, a. :- 2,907,745 15 16 TABLE III. ACTIVE HYDROGEN COMPOUNDS Continued E. POLYESTER RESINS Abbrew. Isocyanate equivalent Compound used in tables Observed. Theoretical

Polyester resin ------PER l---- 246.1 ------(A succinic acid, azelaic acid, ethylene glycol, and glycerol polyester.) Polyester resin ------PER 2---- . 107.4 ------(A. glycerol, azelaic acid and succinic anhydride polyester.) - Polyester resin ------PER 3-...-- 929.0 ------(A diethylene glycol, adipic acid and glycerol polyester.) Polyester resin ------PER. 4.---- 480.5 ------(A diethylene glycol and adipic acid polyester.) (APolyester diethylene resin".------glycol and phthalic anhydride polyester.) PER 5---- 1,046 ------2 In a 3-neck flask provided with a thermometer, a condenser attached through a water trap, and a mechanical stirrer was placed 502 parts succinic anhydride, 943 parts azelaic acid, and 414 parts ethylene glycol. The reaction mixture was gradually heated to 204° C. with continuous agitation at which point a sufficient amount of xylene was added to giye constant refluxing at 195-204°C. After refluxing for 2 hours at 195-204° C., 462 parts of glycerol was added dropwise over a period of 1 hour and 10 minutes. Refluxing was continued for 2 hours and 15 minutes at 204-220°C. at which point most of the xylene was removed by distillation. The viscous syrupy3. As product in the preparation had a nonvolatile of PER, content 1,925 partsof 96.5% of glycerol, and an acid785 partsvalue azelaic of 6. acid, and 418 parts of succinic anhydride Were refluxed with xylene at 184-204°C. for 3%hours. Most of the xylene was removed by distillation at 200-205°C. The viscous syrupy product had 4.a As non-volatile in the preparation content of of 95% PER and 1, acid212 partsvalue ofof diethylene 7.6. glycol, 292 parts of adipic acid, and 2 parts of glycerol were refluxed with xylene at 200-225° C. for 6 hours. The xylene was removed by heating at 220-225°C. with reduced pressure of around 70 80 mm.5. As inThe the viscous preparation syrupy of product PER 1, had212 anparts acid of valuediethylene of 12.8. glycol and 292 parts of adipic acid were refluxed with xylene at 200 225° C. for 6 hours. The xylene was removed by heating at 200-225° C. with reduced pressure of around 70-80 mm. The viscous syrupy6. As product in the preparation had an acid ofvalue PER of 1,87. 212 parts diethylene glycol and 355 gets of phthalic anhydride were refluxed with xylene at 200-225 C. for 6 hours. The xylene was removed byheating at 220-225° C. with reduced pressure of around 70-80 mm. The viscous syrupy product had an acid value of 60. The following examples, presented in tabular form however, the modifier was dissolved in small amounts of to conserve space, illustrate the conversion of mixtures the same solvent for solubility purposes. The mixtures of polybasic acids and polyisocyanates alone and modi- thus obtained were applied to glass panels at 0.002' wet. fied with a monoisocyanate to insoluble, infusible prod- 35 film thickness. The table gives the heat treatment used ucts.designated Each solvent of the to resinous a non-volatile acids wascontent dissolved of 40-60%. in the for conversion andd indicatiindication off filfilm flexibility- - - and wa The isocyanates and modifiers were used in most exam- ter and alkali resistance in actual applications. All parts ples at 100% non-volatile content. In some instances, are by weight.

TABLE IV.-EXAMPLES OF THE INVENTIONASA COATING A. POLY EYDROXY COMPOUNE) Conversion Wittgod in S. Tri- - Fl Ex. No. liphe. Parts Isocya- Parts ethyl- Active Parts Solvent; proper nolic acid nate amine, compound ties H2O 5% aq. parts Time Temp., at NaCH (hrs.) C. 100°C. - at 259 C.

89.7 Budiol---. 39.3 0.5 175 Flexible.-- 16-- 50 89.7 DEG----- 44.8 0.5 175 ---do----- 16-- 50 89.7 IDG 400 32.7 0.5 175 Brittle--- 8 .75 S; EG 1----- 56. 0.5 175 Flexible.-- 16-- .25 0.5 75 Brittle- 1g+ 2. 134.6 Foooo. 2646 0.5 175 Flexible 08 Epon 864-155.8 0.5 175 Brittle--- 16-- 90 89.7 BDIF.---- 49.4 0.5 175 ---do- 16-- 08 89.7 0.5 175 ---do- 2 .25 89.7 0.5 175 ---do- 2 .08 44, 8 0.5 175 ---do. 2 7 89.7 Budiol. 39.3 0.5 175. Flexible 6-- 50-- 107.6 Budiol.----. 31.4 0.5 75 Brittle--- 16-- 50-- - 71.8 HY M. DEG----- 53.7 0.5 75 Flexible 16-- 90 107.6 HY M. PG 400--- 30.8 0.5 175 --do------16-- 90 71.8 Y. M. EG------33.2 0.5 175 ---do------16-- 50- . 89.7 HY M. G------29.5 0.5 175 Brittle--- i8-- 50 44.8 YM PN------14.5 0.5 175 ---do------16- . 90-- 107.6 HY M.-- Epon 1007 144. 0.5 175 ---do------16-- i. 90 44.8 HYM HQ------66.1 0.5, 75 Flexible, 16-- .75 89.7 HYM BDM- 114 0.5 175 Brittle.-- 6-- 90 89.7 MOX Budiol.--- 39.3 0.5 175 Flexible 16-- 50-- 107.6 MO HX. DEG----- 3.4 0.5 175 ---do------12- 6 152.5 MO HX. EG------8.3 0.5 175 --do- 16-- 50-- 89.7 MO HX. G------29.5 0.5 175 ---do- 16-- 28 89.7 MO HX. PN------24.2 0.5 175 ---do- 16-- 90 89.7 MO HX. Epon 864. 55.8 0.5 75 6-- 90 107.4 MO HX- - BDF------34.5 0.5 175 ---do- 16-- 7 53.8 MO HX. R------49.5 0.5 175 -- 16-- 90 71.8 MO HX. DHN 86. 0.5 75 Brittle--- 4. .08 89.7 MO HX. BDM----- 91.2 0.5 175 Flexible 8 8.5 89.7 N 200- Budiol---. 39.3 0.5 175 ---do------16-- .08 89.7. N 200- DEG----. 44.8 0.5 175 Brittle 16-- 25 161.5 N 200--- PG 4000, 32.7 0.5 175 --do------16-- .75 44, 8 N 200----. 266 ------EG------41.5 0.5 175 ---do------16-- .25. 2,907,745 TABLE TV.--EXAMPLES OF THE INVENTIONAS A COATING-Continued - A POLYEYOROXY.COMPOUND-Continued -

-- Conversion . - - - - WithodS. in Ex. No. Diphe. Parts Isocya- Parts ethyl-Tri- Active Parts Solwent properFilm nolic acid nate amine, compound ...... ties HaO 5% aq. "... . - * . . . . . ' parts Time Temp. . , at NaOH (hrs.) C. 100° C. at 25° C. XXXVI. 'N 200. 35.4 MK - 0.5 175 Brittle-...-16-----...-5 XXXVII- MO TM 44.8. MIK. 0.5 175. ---do------16-- 90-- XXXVIII--- MQ N5. 39.3 MTK 0.5 175 ---do------7.5 ... .08 XXXIX MO N5. 33.6 MIK. 0.5 175 -...do- 6.0 ... 8 XL---- MO N5. 46.9 MTK . . 0.5 175 ---do------2.5 .08 - Dur------Budioi. 39.3 MIK. 0.5 175 ---do------7.5 "...08 Dur.----- Epon 864. 233.7. MIK. 0.5 75 - Flexible.-- 8 90-- HY T. Budiol. 19, 6 MEK 0.5 175 Brittle 8 .50 84 EY Epon 1007, 36.0 MK- 0.5 ---do------... -50-- DPCA-248.6 HYT. EG-----. 1.4 MIK. 0.5 .08 OCA 99.1 HY- 16.5 MIK- - 0.5 2.5 DXA.----.84 HY M. 2.7 MK. 0.5 .5 DXA.84 EY MI 17.9 - MIK 0.5 - 175 --do --- 16---. 72-- IDPOA17.9 FY M. 165.2 MIK. 0.5 175. Flexible 16- .08 s DPCA. 17.9. Y. M. 33.0 MK 0.5 175. Brittle 16- . . .72-- DCA 99.1N 200--- 8.9-MK. 0.5 175 ---do------.08 ,08 DPCA-117.9 MOTM 75 - Epon 864 - 62.3 MIK.------0.5 175 ---do------16-- 72-- B. POLYBASIC ACIDS 89.7. HYT. 87.5 0.5 175 Brittle---.5 25.5 44.9 HYT. 71.4 0.5 175 Flexible. 16-- 50-- 89.7 HYT. 57.3 0.5 175 Brittle- 4.5 .25 170.4 BY T 2.6 0.5 75 5 89.7 HYT 83. 0.5 175 22.5 44.9 HYM 43.8 0.5 75 50 44.9. HYM 131.3 0.5 175 50 89.7 HYM 7.4 0.5 175 50 107.6 EY M. 57. 0.5 175 50-- 98.7 EYM 5.6 0.5 175 50 174.9 HY M. 2.6 0.5 175 96-- 89.7 EY M- 83. 0.5 175 50-- 89.7 MO HX. 8.7 0.5 75 50 116.6 MO. HX- 49.9 0.5 75 2.5 89.7 MO HX- 52.4 0.5 175 ... 08 . 34.6 MO. HX- 41.5 0.5 175 08 89.7 N200--- 26.3 0.5 75 .25 TPA-...-- 44.9 N. 200---- 87.5 0.5 175 ..08 DPA--. 9.0 MO. T.M. 1891.8 87.5 0.5 175 ... 08 DPA 89.7. MO N5- 233 1.8 87.5 0.5 175 .08 LXXIII. DPA. 89.7 Dur.--- 67 5.4 43.8 0.5 75 2 .08 LXXIV-----DPA.--- 80.7 Dur------66 7.2 26.2 0.5 175 2. .08 LXXV DXA..... 84 HYT. 54 ------5.7. 50:50 MIKIDioxane. 0.5 75 1.5 .08 LXXVI-DPCA-117.8 HYT. 73 - 5.4 24.9 50:50 MIKIDioxane- 0.5 175 1.5 6 LXXVII DCA-99. HYT-91. 5.4 35.7 50:50 MIKIDioxane- 0.5 175 5 1.5 LXXVII---. DXA.---84 EY M. 126------35.0 50:50 MIKIDioxane. 0.5 175 6 50 LXXIX DCA 99.1 Y.M.-- 84 ------5.7. 50:50 MIKIDioxane- 0.5 175 6- 50 LXXX- DXA.-----84 MO HX-835.4: 21.4 50:50 MIKIDioxane- 0.5 175. 5- .25 -LXXXI DCA 99. MO HX- 83 9.0..I.A. 24.9 50:50. MIKIDioxane 0.5 175 6 1.5 LXXXII. DPCA. - 117.8 MOTM. 65 5.4 A.A.------7.1 50:50 MIK/Dioxane- 0.5 175 Brittle 10 6 . . C. POLYAMINE AND POLYAMDE IXXXII. DPA. 1345. EYT 9.0-50:50 MKTMSO, 0.5 175 Brittle--, 16- . . . 12 ... LXXXIV---- 89.7 HYT. 2.1 50:50 MIKIDMSO. 0.5 175 ---do----- 4. 1, 5 LXXXV 89.7 HYT. 8.3 50:50 MIKIDMSO. 0.5 175 ---do----- 16-- 3. LXXXVI.--- 89.7 HYT. 27 50:50 MIKIDMSO. 0.5 75 25 08 LXXXVII. 89.7 HYT. 3.2 50:50 MIKIDMSO. 0.5 175 .25 4 LXXXVIII 89.7 EY. T 98.6 50:50 MIKIDMSO. 0.5 175 5 1.5 98.7 YT 190 50:50 MIKIDMSO- 0.5 75 14 95 98.6. HYM 5.4 50:50 MIKIDMSO. 0.5 75 Brittle. 16-- 95-H 89.7 YM 10,850:50 MIKIDMSO. 0.5 175 --do--- 16-- 95-- 89.7 EYM 6.4 50:50 MIKEDMSO. 0.5 175 Flexibl 16-- 95 125, 6 HY M. 12.7. 50:50 MIKIDMSO. 0.5 175 Brittle.-- 16- 95 89.7 HYM 8.2 50:50 MIK(DMSO. 0.5 175 ---do. ---- 16- .. 4 44.8 HY M. 380 50:50 MIKIDMSO, 0.5 175 Flexible 16-- 95 116.6 MO HX- 12.6 50:50 MIKIDMSO. 0.5 175. Flexible 16-- 95 89.7 MO HX. 10, 6 50:50 MIKIDMSO-- 0.5 75 -- do----- 16-, 95 89.7 MO HX- 12.5 50:50 MIKIDMSO- 0.5 175 ---do----- 16-- 4.-- 89.7 MO HX. 16.0 50:50 MKIDMSQ-- 0.5 - 175 ---do----- 16-- 21-- 134.5 MO HX- 2.6 50:50 MIKIDMSO. 0.5 175 --- do.---- 16-- 4. 25.6 MOEX- 24.6 50:50 MIKIDMSO. 0. 5. . .75 --do. 14 50 DPAll- 134.6 MOEX. 48.3 50:50 MIKIDMSO. 0.5 175-do--- 16-- 50 DPA. 89.7N 200--- 5.4 50:50 MIKIDMSO. 0.5 175 Britte- 16-- .08 DPA--- 107.6 N 200--- 7.6. 50:50 MIKIDMSO. 0.5 175 ---do----- 25 08

DPA-. 89.7 N. 200- 56.1 50:50 MIKIDMSO. 0.5 175 ". . . .50 DPA 89.7 MOTM- 2.7 50:50 MIKIDMSO. 0.5 175 24 DPA. 89.7 MOTM 19 50:50 MIKIDMSO. 0.5 175 2 DPA 44.8 MOTM. 31.8 50:50 MIKIDMSO. 0.5 75 95 DPA.----- 34.5MON5. 53.1 '0, 5 175 .08

DPA..... 89.7. Durll--- 190 0.5 75 08

DXA-168 EY.T. 9 0.5 175 ,08

DCA 198.3 HYT--- 41 0.5 175 * - 2.5 DCA 198.3 MOX- 12.5 50:50 DMSO/Diox- 0.5 175-doll.-- 17 .08 8tle. 50:50 DMSOIDiox- 0.5 175. Flexible; 16- 40 0.5 175 .08 0.5 175 12 0.5 175 .5 0.5 75 .08 0.5 175 25 Dioxane/MIK.-- 0.5, 175 26.5 2,907,745 19 20 TABLE IV-EXAMPLE OF THE INVENTION AS A COATING-Continued D. SULFUR-CONTAINING COMPOUNDS Conversion Withstood in hrs. Tri- --- Film Ex, No. Dipher Parts Isocya- Parts ethyl- Active Parts Solvent proper nolic acid nate amine,parts compound Time Temp., ties H2Oat 5%NaCE aq. (hrs.) C. 100° C. at - 25°C.

OXXI------TPA----- 17.9 BY T. 82 5.4 T.A.------. 40.6 MIKIDMSO------. 0.5 175 Brittle--- .08 .08 DPA.----- 9.0 HYT. 72 5.4 LP3------418 MIK.------.0 200 Flexible- .08 .08 DPA.---- 44.9 HY M--- 40 ------FGA.-----. 17 MIKITDMSO- 0.5 175 Brittle 16-- 96-- DPAll- 9.0 HYM 70 TU------3.6 MIKIDMSO- 0.5 175. Flexible--, 16-- 96-- DPA---- 44.9 MO X- 62 .5 MIK/PMSO- 0.5 175 --do---- 4. .08 DPA.---- 179.4 IY T. 362 .1 FMIK.------0.5 175 Brittle 16-- DPCA. 259.4 HYT. 109. .9 Dioxane/TDMSO---- 0.5 175 --do----- 75 .08 CXXVIII. DXA 84 HY M. 98 -...------. Dioxane/MIK------0.5 175 Flexible. 16-- 1. CXXXIX. DRCA 65.1 MO HX. 83 .8 Dioxane/MIK- 1.0 200 Brittle, 2.5 .25 CXXX-----. DCA. 99.2 MO TM 65 ------.5 Dioxane.---- 0.5 175 --do----- 16-- 3 CXXXI----- DCA 99.2 N 200--- 106 7.2 .2 Dioxane/MI 0.5 200 Flexible- .08 l E. POLYESTER RESINS

CXXXIII--- DPA----- 27 Y T. 54 ------PER 1.- 73 MIK.------0.5 175 Flexible. 15-- 32 CXXXIII--- DPA- 8 HYT- 109 PER - 73 - MIK. 0.5 175 ---do----- 15.-- 2 CXXXIV-- DPA 108 HYT. 36 PER:1. 73 0.5 175 ---do----- 15- 2 CXXXV DPA----- 35 HYT. 63 PER - 73 0.5 175 --- do----- 15.-- .08 CXXXVI-DPA- 188 HYT. 217 - PER, 73 0.5 175 Brittle-...- 15- 5 CXXXVII 27 82 PER1. 146 0.5 175 Flexible- 15-- 80-- CXXXVIII 10427 10909 ------PER1. 21948 0.5 175 ---do----- 15.--2 80--.06 166 172 48 - 0.5 75 Brittle--, 16-- .25 113 18 48 0.5 175. Flexible. .02 80 97 73. 0.5 175 --...-- do---- .08 7 161 177 43 0.5 175 -...- do... 3 5 22 9. PER 2. 93 0.5 175 -----do---- 16- 32-- 22 45 PER 2. 31. 0.5 175 Brittle. 16-- 23 27 EYM 68 PER1- 29 . 0.5 175. Flexible. 23-- 55-- CXLVIE----- 27 N200 120 PER 46 0.5 175 ---do----- 23-- 55 CXLVIII--- 54 MOTM 485 EPER, 73 0.5 175 Brittle... 15- 8 9 N200--- 27 PER 3- 98 0.5 175 Flexible.-- 12 6.5 99 IYM- 168 PER3. 98 0.5 175 Brittle- 23- 55-- 13 N 200---- 40 PER. 4.- : 73 0.5 175 Flexible. .08 08 161 MOX 202 1.80 PER, 4, 73. 0.5 i.75 ----- do---- 23-- .08 27 MOTM 88 1,80. PER5, 52 . 0,5 175 Brittle--- 23-- 8 45 N200. 133 62 0.5 175 ----- do-...- 23- 8

23 MOBX. 78 62 0.5 175 Flexible-- - 8 25 YT 27 37 0.5 75 120-- 92 MOM 373 PER3 47 Dioxane- 0.5 175 16-- 120-- 84 MOBX. 78 PER2 31 Dioxane- 0.5 175 Flexible. 24-- 1. 34 EYM 84. PER 37. Dioxane- 0.5 i.75 --...-- do--- ió-- 120-- 106 MON5- 58 1.80 PER 4--. 24. Dioxane- 0.5 175 Brittle--- 1 25 95 EIYM--- 68 ------PER, 5 - 52 Dioxane- 0.5 175 ----- do---- 16-- 48-- 247 HYM 182 PER 3--- 47 Dioxane- -- 0.5 175 -----do---- ... 8 08 CLXIII------DC.A.- 50 IN 200---- 3: PER. 2.---- 31 Dioxane- 0.5 175 -----do---- 16- . 120 CLXIV.---- DC.A.--. 50 HY M--- 105 PER 2.-- 62 Dioxane------0.5 175 Flexible--, 16-- 120-- It will be understood that the description of flexibility triethylamine, 369 parts of polyester resin PER 1, and is purely relative and indicates merely whether or not a 272 parts toluene 2,4-diisocyanate. The conversion was substantial part of the film could be peeled or stripped also carried out at 25 C. The product was similar to intact from the panel. Varying degrees of flexibility or that of Example CLXV in that the foam was rigid but brittleness are encompassed by the general descriptive 50 -relatively unbrittle. terms used. Products which might be too brittle for Example CLXVII use on film wherein considerable flexibility was a requi Example CLXV was repeated, except that 181 parts site would nevertheless be useful in films where flexibil of toluene 2,4-diisocyanate, 9 parts of water, and 464 ity is of no importance or in cast or molded articles. 55 parts of the polyester resin designated PER 3 in Table 3 In order to demonstrate the preparation of a foam were employed. Again, the mixture was converted at resin structure in accordance with the invention, the 25 C. The foam that was produced was flexible with following examples were prepared: relatively low rigidity. - In the preceding three examples relating to foam. M Example CLXV products, the polyester resin was at liquid at ordinary 44.9 parts DPA, 15 parts water, 27 parts of polyoxy 60 temperature and was mixed with the DPA by melting ethylene Sorbitan mono-oleate, an emulsifier sold under the latter and stirring. After cooling to room tempera the trade-name "Tween 80” by Atlas Powder Company, tures, the mixture remained sufficiently fluid to be easily and 1.8 parts of triethylamine were stirred with 369 mixed with the isocyanate. Where the mixture of DPA parts of the polyester resin that is designated PER 1 in 65 and active hydrogen compound is not sufficiently fluid Table 3 in an open container until a homogeneous mix at room temperature, it may be heated to its melting ture was obtained. 299 parts of toluene-2,4-diisocyanate point and the reaction allowed to proceed upon the addi were added, with continuous stirring, and the mixture tion of the isocyanate. It is preferred that the foaming allowed to foam freely. The temperature of the mix be allowed to take place at the lowest possible tempera ture was maintained at 25 C. until the product had 70 ture consistent with proper mixing since high tempera Solidified. The result was a rigid foam which was rela tures appear to promote non-uniform cell structure. tively unbrittle. . The aforegoing examples are furnished only for the Example CLXVI guidance of those seeking to practice the invention and Example CLXV was repeated, employing 22.5 parts not for the purpose of defining the boundaries within DPA, 14 parts water, 25 parts "Tween 80,” 1.8 parts 5 which it is operative. Numerous other embodiments 2,907,745 2. 22 tions.are possible and will be suggested by these few illustra 5. The composition of matter as described in claim Having thus described the invention, that which is 4 wherein R of (A) is an organic aromatic radical. claimed is: 6. The composition of matter as described in claim 4 wherein R of (A) is an organic aliphatic radical. 1. A composition of matter comprising the polymeric 7. A method of preparing a new polymeric composi reaction product of (A), a compound of the general tion of matter which comprises admixing (A) a com formula R(NCX), wherein R is an organic radical hav pound of the general formula R(NCX), wherein R is ing a valency equal to z, X is a chalcogen having an an organic radical having a valency equal to Z, X is a atomic weight of less than 33 and z is an integer having chalcogen having an atomic weight of less than 33 and z. a value of more than 1, (B) a compound containing at O is an integer having a value of more than 1, (B) an or least two active hydrogen atoms, each of said active ganic compound containing at least two active hydrogen hydrogen atoms being present in a compound selected atoms, each of Said active hydrogen atoms being present from the group consisting of polyesters, polyhydric alco in a compound selected from the group consisting of poly hols, polyhydric phenols in which the active hydrogen esters, polyhydric alcohols in which the active hydrogen

appears in functional groups consisting of hydroxyl groups, polyamines, polyamides, polycarboxylic acids, 5 appears in functional groups consisting of hydroxyl water, mixtures thereof and any of the above compounds groups, polyhydric phenols, polyamines, polyamides, in which at least one oxygen atom has been replaced by polycarboxylic acids, water mixtures thereof and any of Sulfur and (C) a pentanoic acid consisting essentially of the above compounds in which at least one oxygen atom 4,4 bis(4-hydroxyaryl) pentanoic acid wherein the hy has been replaced by sulfur and (C) a pentanoic acid droxyaryl radical is a hydroxyphenyl radical and is free 20 consisting essentially of 4,4 bis(4-hydroxyaryl) pentanoic from substituents other than alkyl groups of from 1-5 acid wherein the hydroxyaryl radical is a hydroxyphenyl carbon atoms, wherein the reactive functional groups of radical and is free from substituents other than alkyl (A) and (B) -- (C) are present in an equivalent ratio of groups of from 1-5 carbon atoms, wherein the reactive from about 5:1 to 1:5 with (B) constituting from 5 functional groups of (A) and (B) -- (C) are present on 65% by weight of (B) -- (C). 25 an equivalent ratio of from about 5:1 to 1:5, with (B) 2. The composition of matter of claim 1 wherein the constituting from 5-65% by weight of (B) -- (C), and pentanoic acid of (C) consists essentially of 4.4 bis(4- heat converting said mixture to an insoluble, infusible hydroxyaryl) pentanoic acid wherein the hydroxyaryl CS radical is a hydroxyphenyl radical and is free from sub 30 stituents other than alkyl groups of one carbon atom. References Cited in the file of this patent 3. The composition of matter of claim 1 wherein the pentanoic acid of (C) is 4.4 bis(4-hydroxyphenyl) pen FOREIGN PATENTS tanoic acid. 901,768 France ------Nov. 13, 1944 4. The composition of matter of claim 3 wherein the 35 reactive functional groups of (A) and (B) -- (C) are OTHER REFERENCES present on an equivalent ratio of from about 2:1 to 1:2 Bader et al.: “J.A.C.S.," vol. 76, pages 4,465-4, 466 with (B) constituting from 5-65% by weight of (B) (September 5, 1954.) (Copy in Scientific Library.) -- (C). UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,907, 745 October 6, 1959 Sylvan O. Greenlee It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below. Column 4 line 2l for "that" read -- than -- column IO TABLE I Second column thereof, last line of Example No. 3 for "and" read -- an --; columns li and 12, TABLE II, third coium there of the formula opposite Example No. 2 should appear as shown below instead of as in the patent:

OCN

columns lis and ló 17 and 18 and 19 and 20 TABLE IV, second column thereof for the heading "Diphenolic acid" read -- Diphenolic Acid -- same columns l5 to 20, TABLE IV, last column thereof, in the sub-heading for "NaCH' read -- NaOH -- columns l and 18, TABLE IV-C. third column thereof, and opposite "Ex, No. LXXXIX" for "98.7" read -- 89.7 --; columns l9 and 20 TABLE IV-D. first column thereof, for Ex. No. 7 "CXXXIX' read -- CXXIX -- same columns l9 and 20, TABLE IV-E eighth column thereof and opposite "Ex, No. CXLIII" for '43" read -- 73 --; column 22 line l6, strike out " polyhydric phenols' and insert the same after "alcohols" in line l4 same Column 22 Signed and sealed this 8th day of November 1960.

(SEAL) At test : KARL. H. AXLINE ROBERT C. WATSON Attesting Officer Commissioner of Pat et S