MXPA97008424A - A product that contains uretano liquo - Google Patents

Abstract

An adduct containing liquid urethane, a process for the preparation thereof and applications therewith is described. More specifically, this invention relates to a stable adduct which is a liquid at room temperature and which contains a plurality of urethane linkages and, furthermore, which is substantially free of any isocyanate functionality or isocyanate reagent functionality. These adducts can be used as lubricating coolers or surfactant agents

Description

A PRODUCT CONTAINING LIQUID URETHANE This invention relates to an adduct containing liquid urethane, a process for the preparation thereof and applications therewith. More specifically, this invention relates to a stable adduct which is a liquid at room temperature and which contains a plurality of urethane linkages and still being substantially free of any isocyanate functionality or isocyanate reagent functionality. In general, urethane-containing adducts can be prepared by the reaction of organic isocyanates with hydrogen-containing substances. The reaction can be carried in the presence of a solvent and several isocyanate addition sequences with active hydrogen-containing substances employed so that they reach a final product which is substantially free of any isocyanate functionality or isocyanate-reactive functionality Illustrative of said products and various techniques of he reacted n known in the art is that described in U.S. Patent 4,079,028. For many applications including the field of surfactants, for example, when manufacturing polyurethane foams, lubricants or coolers, it is desirable that the adduct be of attractive purity and that it be A liquid For polyurethane applications, the presence of a lower molecular weight adduct can be detrimental to being an anti-foaming agent when it tries to exploit the property of surfactant of a product of higher molecular weight. The liquid characteristic of the adduct is highly convenient since it increases its versatility with respect to applications where stable systems with other substances in the liquid phase are required. Our present investigations are directed to the development of an adduct containing liquid urethane having an improved purity and especially a liquid adduct having a branched structure. From our investigations, it is now found that such adducts can be prepared via a solvent-free process with careful control of the reagents, processing aids and process conditions. By the term "processing aids", substances are understood to act by catalyzing reactions involving the functionality of the isocyanate and especially the substances that promote the formation of the urethane linkage. In a first aspect, this invention relates to a urethane-containing adduct comprising the reaction product of a "monoahl" with an isocyanate-terminated intermediate, the same being obtained by coupling a polyisocyanate with a "polyahl", wherein the adduct is a liquid at room temperature and having an average molecular weight of 600 to 80000, is substantially free of any isocyanate functionality or any functionality of isocyanate reagent.

In a second aspect, this invention relates to a urethane-containing composition that is a liquid at room temperature, the reaction product being a "monoahl" with an isocyanate-terminated intermediate obtained by coupling a polyisocyanate with a " polyahl "which is based on total present moles of components (a), (b) and (c) and to a total of 100 percent, comprises: (a) from 65 to 100 mole percent of an adduct of the structure general (I); B- (A-M), (I) (b) less than 35 to 0 mole percent of an adduct of the general structure (II); and M-A-M (II) (c) of less than 12 to 0 mole percent of an adduct (III) containing two or more B-portions per molecule, M-A- (B-A) n-B-A-M (III) wherein n > 1 wherein A is derived from polyisocyanate; B is derived from "polyahl"; M is derived from "monoahl"; and f is the number of isocyanate reactive groups formally present in the "polyahl". In a third aspect, this invention relates to a solvent-free two-step process A for preparing an adduct containing a plurality of urethane ligatures which are a stable liquid to room temperature and which are substantially free of isocyanate or isocyanate-reactive groups, comprising the reaction in a first step of a polyisocyanate with a polyhal to provide a finished intermediate in socianate and in a second step reacting said intermediate with a "monoahl", wherein: a) the polyisocyanate comprises at least two isocyanate moieties / molecule with a relative reactivity other than "polyahl"; b) "polyahl" is an organic substance having a molecular weight of 200 to 20,000 and containing per molecule two or more isocyanate-reactive functional groups which are -OH, -SH, or -NHR wherein R is hydrogen or I rent; c) the "monoahl" is an organic substance that contains an isocyanate-reactive functional group being -OH, -HS, -COOH or -NHR wherein R is hydrogen or alkyl characterized by: i) for the first step, carried to performed essentially under anhydrous conditions and in the absence of a urethane promoter catalyst, the "polyahl" is added at a controlled rate to the polyisocyanate so that the reaction temperature does not exceed 100 ° C and the total amount of polyhal added is an equivalent stoichiometric or less with respect to the polyisocyanate; Y ii) for the second step, the "monoahl" is added in a restricted amount sufficient to consume all the isocyanate groups wherein said amount is determined by directly monitoring the reaction mixture for the presence of isocyanate functionality. In a fourth aspect, this invention relates to an isocyanate-terminated intermediate obtained by contacting it essentially under anhydrous conditions and in the absence of a urethane-promoting catalyst, a "polyahl" having a molecular weight of 20 to 20000 and containing two or more isocyanate-reactive functional groups per molecule which are -OH, -SH, -COOH, or -NHR wherein R is hydrogen or alkyl, with a polyisocyanate comprising at least two portions of isocyanate / molecule with a different reactivity than "polyahl", where the "polyahl" is added at a controlled rate to the polyisocyanate so that the reaction temperature does not exceed 100 ° C and the total amount of "polyahl" added is a stoichiometric equivalent or less with respect to the polyol. isocyanate and the resulting intermediate, wherein said intermediate has an isocyanate content of 0.5 to 5 weight percent based on the total present weight of the components (a), (b) ) and (c) to a total of 100 percent, comprises: (a) from 65 to 100 molar percent of an adduct of the general structure (IV); B (-A) f (IV) (b) less than 35 to 0 mole percent of an adduct of the general structure (V); and A (V) (c) of less than 12 to 0 mole percent of an adduct (VI) containing two or more B portions per molecule, wherein A is polyisocyanate; B is "polyahl"; and f is the number of reactive isocyanate groups formally present in the "polyahl". In yet another aspect, this invention relates to the use of the adduct, or composition thereof, as a lubricant, cooler, hydraulic fluid, paint thickener, or surfactant. Said cooling and lubricating agents fvalue, for example, in the processing stry, where they can be used in aqueous or non-aqueous conditions. Surfactants or surfactants fvalue in the manufacture of cellular polyurethane polymers. When the adduct is used as a hydraulic fluid, it is advantageous to present it in an amount of 1 to 50, preferably 1 to 25 percent by weight, based on the total weight of the hydraulic fluid including adduct, and including any water present. When the adduct is employed as a paint thickener, it is advantageously present in an amount of 0.1 to 10, preferably 1 to 10 weight percent, based on the total weight of the adduct paint composition.

The adduct product of this invention is a substance, substantially free of any isocyanate functionality or any isocyanate reactive group including hydroxyl, thiol, carboxylic acid, thiocarboxylic acid, or primary amine functionality. The adduct is a liquid at room temperature (25 ° C) and comprises a plurality of urethane linkages. The adduct can be represented by the structural formula (I). B- (A-M), (I) where A is derived from polyisocyanate; B is derived from "polyahl"; M is derived from "monoahl"; and f is the number of isocyanate reactive groups formally present in a "polyahl". It should be appreciated that the bond A-B and A-M will be a urethane ligation as derived from the reaction of an isocyanate group with an isocyanate reactive group, eg, a hydroxyl group.

When the adduct is based on a difunctional "polyahl" it will have a linear structure; when they are based on a triol, it will have a branched or three-limbed structure and so on. For each polyisocyanate entity (A) incorporated in the adduct, at least two urethane linkages were introduced. With reference to the process for preparing said liquid adducts, which will be discussed in detail below, the product of this invention will in most cases be a composition comprising predominantly an adduct of structure (I), with smaller amounts of adducts corresponding to Structures (II) and (III). Adduct II corresponds to a polyisocyanate (A) reacted completely with a "monoahl" (M); adduct III corresponds to a structure containing two or more "polyahl" entities (B) per molecule. It should be appreciated that adduct III may require a highly complex, branched structure when functionality B is greater than 2, where each branch will nominally be terminated with an entity derived from "monoahl". By way of example, the structures of Adducts II and III are given below, in this case (III) comprising two or more portions B are described as a linear adduct originating through the "polyahl" containing two groups reactive with isocyanate / molecule. M - A - M (II) M - A - (BA) "- B - A - M (III) where n _1 An adduct corresponding to structure (II) can result when the polyisocyanate reacts only with" monoahl "; an adduct corresponding to Structure (III) can result when multiple polyisocyanate molecules are capable of reacting with multiple molecules of "polyahl" before the reaction with "monoahl". The liquid urethane-containing adduct product of this invention can be characterized in that it has an average molecular weight of 600 to 80000, preferably 1000 to 60000 and more preferably from 2000 to 30000 The compositions comprising the adduct mentioned (I) are further characterized by the presence of substances corresponding to Structures (II) and (III), which is based on the total molar amount of said substances present, comprising: for (I), at least 65, preferably at least 75, more preferably, at least 90, and up to 100 mole percent, for (III), less than 35, preferably less than 25, more preferably less than 15, and still more preferably 0 mole percent and for (III), less than 12, preferably less than 10, more preferably less than 7, even more preferably less than 5 and even more preferably 0 mole percent In a preferred embodiment the composition of the adduct may comprise substances (I), (II), and (III) in the molar percentage varies from 65 to 90: from 30 to 5: from 6 to 1 respectively, wherein the total is up to 100. By reference, for good purity, it is It is understood that the final product has a low content of adducts represented by the structures (II) and (III). During the present investigation it has been found that if the presence of the substances of structure type (III) can be minimized, then the resulting adduct will most likely have a liquid characteristic at room temperature and especially when the "polyah" is used in the preparation of the adduct formally contained three or more reactive groups of the socianate / molecule. The composition of the adduct refers to the manufacturing process and particularly to the method of preparing the intermediate product, "polyahl" and polyisocyanate, before the reaction with "monoahl". The adduct of this invention can be prepared by a solvent-free process comprising a first step wherein the polyisocyanate is reacted in the absence of a urethane promoting catalyst, with a "polyahl" containing isocyanate reactive groups to provide an intermediate terminated in isocyanate; and subsequently in a second step, by reacting the isocyanate-terminated intermediate with a "monoahl" to provide the final product. The intermediate can be characterized in that it has an isocyanate content of 0.5 to 5, preferably 1 to 4 percent by weight and a composition comprising the structures (IV), (V), and (VI) represented by the structural formulas: B (-A), (IV) A (V) A- (BA) "- BA (VI) where p >; 1 wherein: A is derived from polyisocyanate; B is derived from "polyahl"; and f is the number of reactive isocyanate groups formally present in the "polyahl". The proportions and quantities of (IV), (V) and (VI) are as given for (I), (II) and (III). Again, in this case for the purpose of clarity, adduct VI was described with a linear structure. However, as discussed for adduct III, it should be appreciated that adduct VI it can also have a highly complex branched structure. A more detailed description of reagents and processing parameters are given below. The polyisocyanate The polyisocyanate used in the process for preparing the adduct has at least two isocyanate moieties / molecules that can be distinguished by a relative difference in reactivity. The difference in reactivity helps to optimize the obtaining of a product that has a narrower molecular weight distribution and reduces the potential for the formation of substrates corresponding to structures (III) and (VII). Suitable polyisocyanates can be aliphatic or preferably aromatic polyisocyanates and especially aromatic di-isocyanates A further advantage for using aromatic diisocyanates, wherein the relative reactivities of the individual isocyanate groups are different, ie, allows the amounts of polyisocyanate (V ) free, unreacted, may be present in the finished isocyanate intermediate for limited by the subsequent advantage of material requirements for the second step of the process and in addition to the value of the adduct in final applications Illustrative of suitable aromatic polyisocyanates include toluene di-isocyanate, methylene diphenylisocyanate and methylene polyphenylisocyanates. are poh-isocyanates comprising isomers of toluene diisocyanate, diphenisocyanate methylene or mixtures thereof. In a highly preferred embodiment, for reasons of relative isocyanate reactivity, it is 2,4'-methylene diphenylisocyanide and especially is 2,4-toluene di-isocyanate, or mixtures comprising said di-isocyanate. The "polyahl" The "polyahl" used in the process comprises two or more isocyanate reagent functional groups per molecule wherein said functional groups include -OH, -SH, -COOH, or -NHR, R being hydrogen or an alkyl portion . Preferred are "polyahls" that have -OH functionality. The "polyahl" may contain up to 8 such functional groups per molecule, the use of "polyahls" containing from 2 to 8, preferably from 3 to 8, and more preferably from 3 to 6 functional groups per molecule is preferred. The "polyahl" used in the process of this invention has a molecular weight of 200 to 2000. The molecular weight of the "polyahl" is preferably 50, more preferably 1000 and even more preferably 2000; and preferably up to 15,000 and more preferably up to 1000. In a preferred embodiment, the "polyahl" is a polyester or particularly a polyoxyalkylene polyol wherein the oxyalkylene entity comprises oxyethylene, oxypropylene, oxybutylene or mixtures of two or more thereof, including, especially mixtures of oxypropylene-oxyethylene. Alternative polyols that can be used in the invention include polyols based on polyalkylene carbonate and polyols based on polyphosphate. The nature of the selected polyol depends on the desire of imparting or not some water solubility to the adduct, which may be advantageous for certain applications. The solubility in water can be increased by selection of polyols having a lower molecular weight or a high oxyethylene content. Suitable polyoxyalkylene polyols are exemplified by various commercially available polyols as used in polyurethane, lubricant, surfactant applications and include polyoxypropylene glycols designated as VORANOL ™ P-2000 and P-4000 with molecular weights of respectively 2000 and 4000; polyoxypropylene-oxyethylene glycols such as DOWFAX ™ DM-30 is understood to have a molecular weight of 600 and an oxyethylene content of 65 weight percent and SYNALOX ™ 250-700 is understood to have a molecular weight of 5500 and a content of oxyethylene 65 weight percent, all available from The Dow Chemical Company; polyoxyethylene triols available under the TERRALOX ™ brand and designated as product of WO-98 and WG-16 is understood to have a molecular weight of 700 and 980, respectively, polyoxypropylene-oxyethylene triols designated as VORANOL ™ CP 10001 and CP 3055 is understood to have respectively a molecular weight of 1000 and 3000 and VORANOL ™ CP 3001 is understood to have a molecular weight of 3000 and an oxyethylene content of 10. percent by weight and VORANOL ™ CP 6001 is understood to have a molecular weight of 6000 and an oxyethylene content of 15 weight percent, all available from The Dow Chemical Company. polyoxypropylene hexoles that include TERRALOX ™ HP-400 is understood to have a molecular weight of 975, both available from The Dow Chemical Company, higher functionality polyether polyols including those based on carbohydrate initiators such as, for example, sucrose and exemplified by VORANOL ™ 370 available from The Dow Chemical Company The "monoahl" The "monoahl" used in the process is an organic substance that contains an isocyanate-reactive functional group per molecule that is -OH, -SH, -COOH or -NHR wherein R is hydrogen or alkyl A monohal having as the isocyanate reactive functionality a hydroxyl group, hereinafter referred to as a monol In addition to the isocyanate reactive functional group, the monol may optionally contain the alternative functionality, which, under The conditions of the present invention are not considered to be reactive with isocyanate. Illustrative of said alternative functionality may be alkene, alkyne, The monol used in the process is chosen with consideration towards the intended final application. When it is desired to influence, for example, the water miscibility of the adduct product, an appropriate hydrophilic or hydrophobic monohal is used. Any hydrophilic / hydrophobic characteristics introduced in a manner The "polyahl" will also contribute to the overall characteristics of the adduct. Similarly, when it is desired to exert additional control of for example, the surfactant properties of the adduct, a branched monohal or an appropriate fluorine or silicone is chosen. The preferred monools for use in this invention are pohoxyalkylene monools with a molecular weight of 150 to 6000 preferably 250, more preferably 500, even more preferably of 1000, and preferably up to 5000, more preferably up to 4000. The oxyalkylene entity of the monol oxyalkylene entity comprises oxyethylene, oxypropylene, oxybutylene or mixtures of two or more as an alternative for monohals based on pohoxyalkylene, or monools , the active substances containing polycarbonate, polysiloxin or po-phosphate moieties can also be used. In a preferred embodiment of this invention the polyisocyanate is toluene di-isocyanate comprising, substantially isomer 2, the "polyahl" is a polyole ! of polyoxyalkylene especially a polyol of polyethylene-oxypropylene containing from 3 to 6 hydroxyl groups, and the "monoahl" is a polyoxyalkylene monol especially containing oxybutylene groups Particularly preferred monools, when it is intended to increase the hydrophobic characteristics, are those comprising the oxybutylene entity, spatially in an amount of more than 50 weight percent by the total weight of the monol The Process The method for preparing the urethane-containing adduct is a two-step process comprising a first and second step optionally between the first and second step there is an intermediate step. The first step relates to the preparation of an isocyanate-terminated intermediate by reacting the poh-isocyanate with the "polyahl" at a reaction temperature not exceeding 100 ° C, in Essentially Anhydrous Conditions Essentially by anhydrous conditions, it is understood to be less than 1500, preferably less than 750, more preferably less than 350 ppm of water. The reaction temperature is advantageously 20 ° C, more preferably 35 ° C, and preferably up to 80 ° C. C, more preferably up to 70 ° C. The operation in said temperature scale, provides an optimum reaction regime without losing the difference in the relative reactivities of the individual isocyanate groups of the polyisocyanate. At higher temperature, the beneficial effect of the relative isocyanate reactivities can be substantially decreased and additionally the isocyanate can be consumed by an area Undesirable allophanate production The "polyahl" is added to a controlled regime for the po -isocyanate so that the reaction temperature does not exceed 100 ° C with the total amount of "polyahl" added being a stoichiometric equivalent or less relative to the po -isocyanate The total amount of the "polyahl" advantageously does not exceed 099, preferably does not exceed 095 of an equivalent, and advantageously is of at least 04, preferably of at least 06, and more preferably of 0 85 of one equivalent per equivalent of isocyanate In a modality highly preferred when the "polyahl" is a polyol is present in a total amount corresponding to 0.85 to 0.95 of an equivalent. As already mentioned, the first step of the process is carried out essentially under anhydrous conditions and in the absence of a processing aid, as defined above. To minimize potential gel formation, or even solidification, it is advantageous to use "polyahls" that do not contain any oxyalkylation catalyst or residues that the catalyst had, eg, potassium acetate, which can promote urethane formation or dimerization or trimerization of isocyanate. Additionally to minimize gel formation when preparing the intermediary it is advantageous to use "polyahls", especially polyols, having an acid content, said methods, when preparing isocyanate-terminated prepolymers, are known from the art not generated. they need to be described further. In the course of the present investigations, it is found that the absence in the first step of the process, of a catalyst that promotes urethane, is particularly advantageous with respect to exercising some control in the formation of substances corresponding to Structure (VI) and optionally the structure (III) of the adduct composition. When the resulting isocyanate-terminated intermediate has an unreacted, free, higher isocyanate content, corresponding to Structure (V) and before proceeding to the second In the process step it may be advantageous to reduce said content, for example, by distillation or extraction techniques using suitable solvents including pentane or hexane. The unreacted free di-isocyanate can participate in the second step of the process by providing capped products, the presence of which in the final product can be detrimental to performance in certain applications. In the second step of the process, the intermediary terminating in socianate is reacted with a controlled amount of a "monoahl" to provide the adduct. The controlled amount is such that it essentially converts all socianate functionality without leading to the accumulation of any isocyanate reagent functionality in the final adduct product. The amount required to achieve this result is determined by adding in increments the "monoahl" and directly monitoring the reaction mixture for the presence of free reactive functionality, in this case, isocyanate functionality. The addition is increased continuously until the presence of isocyanate functionality is reduced to a minimum or zero, without accumulation of any other isocyanate reagent functionality. In the process of the present invention it is preferred to employ in-line, in-line spectrometry techniques. Especially valuable is the infrared spectrometry that allows the easy observation of the presence of isocyanate functionality observing the absorption at wavelengths, for example, from 2200 to 2300 cm'1. The Observation at other wavelengths, for example, near IR frequencies is also possible The use of a Fourier transfer infrared spectrometer provides a convenient means of rapid observation for isocyanate functionality directly in the reaction vessel thus avoiding the need to take isolated samples Therefore traditional methods of monitoring the material that involve isolation and subsequent reactive chemical analysis are avoided, for example, by titration, it is properly subject to operator error. For the second step, the temperature of the process it rises for convenience of reaction time and may be greater than 100 ° C without impairing the performance of the adduct in final applications. In general, extended exposure to a temperature greater than 100 ° C should be minimized in order to avoid reactions undesirable side effects that include allophanate formation The intermediary reaction finished with isocyanate with the "monoahl", if desired, can be accelerated by the use of a suitable urethane promoter catalyst Representative of said catalysts include tertiary amine compounds and organotin compounds as used when preparing, for example, polyurethane foam by the reaction of a polyurethane. isocyanate with a poly ol The two-step process described above is the preferred method for manufacturing the adduct since it provides the possibility of manufacturing a non-miscellaneous intermediate masterbatch that can be reacted with several selected "monoahls" to provide adducts suitable for different application areas. Other methods can be envisaged including for example, first reacting the "monoahl" with polyisocyanate to provide an isocyanate-terminated intermediate and subsequently reacting it with the "polyahl". In such an alternative reaction sequence, it will be necessary to adapt the in situ method in direct line, in such a way that it provides monitoring of the amount of "polyahl" and that avoids the accumulation of reactive portions for isocyanates yet does not lead to any isocyanate functionality without reacting The invention is illustrated by the following examples in which all parts and percentages are by weight, unless stated otherwise. Example 1 (absence of catalyst in the first step) This example teaches the preparation of an adduct by first reacting 2,4-toluene di-isocyanate (95% purity, 5% 2,6 isomer) in a polyoxypropylene-oxyethylene triol initiated by glycerin (molecular weight 2150, EO content of 52% by weight, random) to provide an intermediate product that is subsequently reacted with a polyoxybutylene monoalcohol of molecular weight 500, SYNALOX ™ OA-15 available from The Dow Chemical Company 20.2 parts of toluene di-isocyanate were introduced into a closed reactor equipped with an agitator, nitrogen supply, FTIR immersion probe and external temperature control chimney. The toluene di-isocyanate was brought to a temperature of 50 ° C and 75 parts of polyol added in increments at a rate such that the content of the reactor does not exceed 60 ° C. The polyol is present in an amount of 0.45 of one equivalent per equivalent of polyol isocyanate. To complete the addition of the polyol, 0.6 parts of dibutyltin dilaurate were added, followed by rapid additions of the polyisobutylene monoalcohol until the FTIR spectrum indicated no absorption at 2273 cm "1 (isocyanate band). * addition of a total of 56.95 parts of polyoxybutylene monoalcohol no isocyanate absorption was observed in the IR spectrum.The resulting product is a stable liquid at room temperature having a molecular weight of 4140, and being substantially free of end groups of isocyanate or hydroxyl Example 2 (absence of catalyst in the first step) In this example, the same reagents and general procedure have been used as given for Example 1, but with a reverse addition sequence In the first step, 20.2 2,4-toluene di-isocyanate portions were reacted with a total of 56.95 parts of the polyoxybutylene monoalcohol. The reaction was carried out in the presence of 0.6 parts of dibutyltin dilaurate with the polyoxypropylene-oxyethylene triol initiated with glycerin. The polyol was added in increments until no isocyanate absorption was observed in the IR spectrum, which occurred after the addition of a total of 120 pairs of polyol. He The resulting product is a liquid, but it is observed that it has a hydroxyl content. Comparative Example A (with catalyst in the first step) In this example, the same reagents and general procedure as given for Example 1 have been used. In the first step, 20.2 parts of 2,4-toluene di-isocyanate is used. they were mixed with 0.6 parts of dibutyltin dilaurate and the mixture brought to a temperature of 50 ° C and the addition of increased polyol started. After the addition of the polyol to a total amount of only 55 parts, the synthesis process was terminated due to gel / solid formation. Comparative Example B (with catalyst in the first step) In this example, the same reagents and general procedure were used as given for Example 1, but with a reverse addition sequence. In the first step, 20.2 parts of 2,4-toluene di-isocyanate were mixed with 0.6 parts of dibutyltin dilaurate and the mixture was brought to a temperature of 50 ° C before adding an increase of a total of 56.95 parts of plioxybutylene monoalcohol for a period of one hour. Subsequently, a total of 75 parts of the polyoxyethylene-oxypropylene polyol were added increasingly to the product of the first step. After 40 minutes, the viscosity of the mixture began to increase and shortly thereafter a gelified, solid product resulted.

Examples 1, 2 and Comparative Examples A and B demonstrate the importance of having in the first step of the process the absence of a catalyst that promotes urethane. The examples also demonstrate the value of first reacting the polyisocyanate with "polyahl" and then subsequently reacting the intermediate with a "monoahl". Example 3 In order to obtain a better understanding of the role of dibutyltin dilaurate in the preparation process, a series of isocyanate-terminated intermediates has been prepared. A series of isocyanate-terminated intermediates was prepared using the general procedure as given in Example 1, first step, by reacting 2,4-toluene di-isocyanate (95% purity) with a polyoxyethylene-oxypropylene diol ( molecular weight 4000, EO content 50% by weight, mainly hydroxyl content> 70%) in the absence of a catalyst that promotes urethane. The ratio of polyol to polyisocyanate is such that it provides 0.91, 0.77, 0.66, 0.5 and 027 equivalent polyol per equivalent of polyisocyanate. The resulting intermediate compositions are analyzed using the analytical techniques of R N of 13 C to establish the proportion of products corresponding to structures (IV), (V) and (VI). A parallel comparative series of isocyanate-terminated intermediates is prepared from the same reagents in the same proportions but in the presence of a catalyst, dibutyltin dilaurate. Table 1 reports the observations, for which the following notes can be made. With a desire to increase the formation of substances corresponding to Structure (IV) it is advantageous to employ the polyol in an equivalent amount approaching that of the polyisocyanate. At equivalency regimes the presentation of free polyisocyanate is reduced (Structure 'V), however, it was observed that the presentation of an extended chain substance (VII) is increased. The presence of these substances is that which corresponds to the structure (VI) that generally causes the gelling or solidification of the product, especially when using reagents of superior functionality. From the comparison of procedures conducted in the presence and absence of catalyst, it is found that the presence of catalyst favors the undesirable formation of substances of the structure type (VI). Consequently, in this invention, the catalyst promoting the urethane in the first step of the process should not be present. It is also surprisingly found, when the polyol is employed in an amount of more than 0.8 equivalents per equivalent of polyisocyanate, that in the absence of catalyst a greater formation of the desired intermediate (IV) is observed. Although intermediates prepared in the absence of a catalyst may have a higher free pol i-isocyanate content (V), said substance may be removed optionally as discussed above providing an intermediate composition in which the amounts of the undesirable substance (V) have been significantly reduced.

NJ CO It is not an example of this invention Example 4 A number of liquid urethane-containing adducts have been prepared, according to the general procedure of an Example 1 using different polyisocyanate, "polyahls" and "monoahls". Table 2 summarizes the adducts that have been prepared.

Polyisocyanate A: 2,4-, 2,6-toluene diisocyanate (95: 5) "Polyahl" A: a polyoxypropylene-oxyethylene diol of molecular weight of 4000 with an oxyethylene content of 40 weight percent "Polyahl" B: a polyoxypropylene-oxyethylene triol of molecular weight of 2150 with an oxyethylene content of 50 percent by weight, randomly distributed "Polyahl" C: a polyoxypropylene-oxyethylene hexol of molecular weight of 5125 with an oxyethylene content of 50 percent by weight, distributed randomly "Monoahl" A: C6F13CH2CH2OH "Monoahl" B: Dodecanol "Monoahl" C: a polyoxybutylene product initiated with butanol of molecular weight of 500. "Monoahl" D a polyoxybutylene product initiated with butanol of molecular weight of 2000. "Monoahl "E is an oxypropylene adduct of molecular weight of 650 of a polyoxyfluoropropane alcohol. "Monoahl" F a triemethylsilyl-hydroxyethoxypropyl-polydimethylsiloxane oligomer with molecular weight of 1000 EXAMPLE 5 The lubrication performance of Products 4.9 and 4.10 have been compared to that of the commercially available fluids SYNALOX ™ 50-3008 and SYNALOX ™ 100-0280 . BFD observations (in accordance with DIN 51834): Product 4.9: viscosity, 5300 cSt at 40 ° C friction 0.13 mu maximum load 730 Newton Product 4.10: viscosity, 8500 cSt at 40 ° C friction 0.13 mu maximum load 680 Newton SYNALOX ™ 50-3008 friction 0.12 mu Maximum load 400 Newton SYNALOX ™ 100-D280 friction 0.12 mu Maximum load 450 Newton Test of Four Ball Brands (in accordance with DIN 51350): Product 4.9: no mark was detected (<0.1 mm) Product 4.10 no mark was detected (<0.1 mm) SYNALOX ™ 50-3008 0.55 mm mark SYNALOX ™ 100-D2800 0.59 mm mark In the observations of BFD (rolling, friction, wear), normally increases friction with viscosity, adducts of this invention having high viscosity were found. This finding provides a possibility of end uses of high temperature or cooling lubrication. Further observation of little or no marking formation indicates that the products of this invention exhibit excellent film formation under operating conditions.

Example 6 In this example, the ability of the products of this invention to function as surfactants in the preparation of rigid polyurethane foam was demonstrated. The polyurethane foam was prepared using a low pressure machine with the following given formulation. The foam was prepared. of polyurethane having a molded density of 30 to 32 kg / m 3 and the cell size and thermal insulation performance observed 100 pbp of oxypropylene adduct of sorbitol and glycepine having an average hydroxyl number of 261 1 pbp N, Nd? met? lc? clohex? lam? na 0 10 pbp NIAX A-1, a urethane catalyst based on Amine property of Osi 06 pbp CURITHANE 205, a urethane catalyst based on the amine property of The Dow Chemical Company 4 0 pbp water TENSITIVE AGENT - several, see the following Table 152 pbp VORANATE M220, a polymeric MDI available from The Dow Chemical Company (Index 120) The observations reported in the attached table clearly demonstrate the capacity, under non-optimal conditions, of the products of this invention to function as surfactants Surfactant L6900 is commercially available from silicone-based tersoactive agent used when preparing polyurethane foam.

Claims (9)

1. CLAIMS 1. A urethane composition that is a liquid at room temperature, the reaction product being a "monoahl" with an isocyanate-terminated intermediate obtained by coupling a poly-isocyanate with a "polyahl", which is based on in the total moles present of components (a), (b) and (c) for a total of 100 percent, it comprises: (a) from 65 to 100 mole percent of an adduct of the general structure (I); B- (A-M) f (I) (b) less than 35 to 0 mole percent of an adduct of the general structure (II); and M-A-M (II) (c) of less than 12 to 0 mole percent of an adduct (III) containing two or more B-portions per molecule, M-A- (B-A) n-B-A-M (III) wherein n > .1 wherein A is derived from polyisocyanate; B is derived from "polyahl"; M is derived from "monoahl"; and f is the number of isocyanate reactive groups formally present in the "polyahl".
2. 2. A solvent-free two-step process for preparing an adduct containing a plurality of urethane bonds being a stable liquid at room temperature and being substantially isocyanate-free or isocyanate-reactive groups, comprising the reaction in a first step of a polyisocyanate with a "polyahl" to provide an intermediate terminated in isocyanate and in a second step by reacting said intermediate with a "monoahl", wherein: (a) the polyisocyanate comprises at least two isocyanate moieties / molecule with a relative reactivity other than "polyahl"; (b) "polyahl" is an organic substance having a molecular weight of 200 to 20,000 and containing per molecule two or more isocyanate-reactive functional groups which are -OH, -SH, or -NHR wherein R is hydrogen or alkyl; (c) the "monoahl" is an organic substance that contains an isocyanate-reactive functional group being -OH, -SH, -COOH or -NHR wherein R is hydrogen or alkyl characterized in that: i. for the first step, carried out essentially under anhydrous conditions and in the absence of a urethane promoter catalyst, the "polyahl" is added at a controlled rate to the polyisocyanate so that the reaction temperature does not exceed 100 ° C and the total amount of added polyhal is a stoichiometric equivalent to or less than the polyisocyanate; Y ii) for the second step, the "monoahl" is added in a restricted amount sufficient to consume all the isocyanate groups wherein said amount is determined by directly monitoring the reaction mixture for the presence of isocyanate functionality.
3. 3. The process of claim 2, wherein the polyisocyanate comprises an aromatic di-isocyanate that includes 2,4-toluene diisocyanate or 2,4'-methylene diphenyl isocyanate.
4. 4. The process of claim 3, wherein the "polyahl" is a polyoxyalkylene polyol having a molecular weight of 100 to 15000 and contains per molecule of 2 to 8 hydroxyl groups and comprising in the oxyalkylene portion an oxyethylene, oxypropylene, oxybutylene linkage, or mixtures of two or more thereof.
5. 5. The process of claim 3, wherein the first step of the total stoichiometric amount of "polyahl" added is 0. 5: 1 to 1.0: 1 equivalents per equivalent of polyisocyanate.
6. 6. The process of claim 3, wherein for the first step, a polyisocyanate comprising 2,4-toluene diisocyanate or 2,4-methylene diphenylisocyanate is reacted at a temperature of 20 ° C to 80 ° C. ° C, with a "polyahl" being a polyoxyalkylene polyol having a molecular weight of 1000 to 15,000 and containing per molecule of 2 to 8 functional groups of -OH and wherein the total amount of added polyol is 0.85: 1 at 0.95: 1 equivalents per equivalent of polyisocyanate.
7. 7. The process of claim 3, wherein the "monoahl" is a substance containing -OH, being a polyoxyalkylene monol having a molecular weight of from 250 to 6000 and wherein the oxyalkylene entity comprises oxyethylene, oxypropylene, oxybutylene or mixtures of two or more thereof.
8. 8. An isocyanate-terminated intermediate obtained by contacting under essentially anhydrous conditions and in the absence of a catalyzed urethane promoter, a "polyahl" having a molecular weight of 200 to 20,000 and containing per molecule two or more reactive functional groups of isocyanate being of -OH, -SH, -COOH, or -NHR wherein R is hydrogen or alkyl, with a polyisocyanate comprising at least two isocyanate / molecule moieties with a different reactivity to the "polyahl", wherein the " polyahl "is added at a controlled rate to the polyisocyanate so that the reaction temperature does not exceed 100 ° C and the total amount of" polyahl "added is a stoichiometric equivalent or less with respect to the polyisocyanate and the resulting intermediate, wherein said intermediate has an isocyanate content of 0.5 to 5 weight percent based on the total present weight of components (a), (b) and (c) to a total of 100 percent, comprises: (a) ) from 65 to 100 mole percent of an adduct of the general structure (IV); B (-A), (IV) (b) less than 35 to 0 mole percent of an adduct of the general structure (V); and A (V) (c) of less than 12 to 0 mole percent of an adduct (VI) containing two or more B portions per molecule, wherein A is polyisocyanate derivative; B is derived from "polyahl"; and f is the number of reactive isbcianate groups formally present in the "polyahl".
9. 9. The adduct of claim 1, or composition of claim 2, for use as a lubricant, cooler, hydraulic fluid, paint thickener or surfactant.