MXPA97002550A - Process for preparing amidas de ac - Google Patents

Abstract

A process for preparing acid amides, including 1,3,5-triazines with isocyanate functional groups and isocyanate-based 1,3,5-triazine derivatives, is described from the reaction of (amino substituted with Si, Ge or Sn) -1,3,5-triazines and halides deáci

Description

PROCESS TO PREPARE ACID AMIDAS BACKGROUND OF THE INVENTION Field of the Invention This invention relates to the preparation of acid amides by reacting (amino substituted with Si, Ge or Sn) - 1, 3, 5-triazines, such as (N-silylated atino) -1,3,5-triazines, with acid halides.

DESCRIPTION OF THE RELATED TECHNIQUE Several derivatives of amino-1,3,5-triazines amino-1,3,5-triazines are described in the literature for use in a wide variety of fields. Certain of these derivatives / such as alkoxymethyl derivatives of melamine and guanamines, are useful as crosslinking agents or reactive modifiers in curable compositions containing resins having active hydrogen groups. While the alkoxymethylated melamines and guanamines provide excellent results in a number of aspects, they also have the REF: 2í27t ?. disadvantage of releasing aldehyde as a volatile by-product under the curing conditions. For a long time it has been an industry desire to find acceptable alternatives that do not emit formaldehyde in healing. One of these alternatives that has shown great promise is 1, 3, 5-triazines with carbamate and isocyanate functional groups described in US Patent No. 4,939,213, US Patent No. 5,084,541, US Patent No. 5,288,865, EP-A-0604922 , EP-A-0624577, EP-A-0649842, U.S. Patent Application Serial No. 08 / 239,009 (filed May 6, 1994), and U.S. Patent Application Serial No. 08 / 286,835 (filed on August 5, 1994), all of which are common property and are hereby incorporated by reference herein as if they were fully disclosed. The 1,3,5-triazines with carbamate and isocyanate functional groups described in these references have been found to be particularly useful as agents; of crosslinking in coating compositions based on resins with hydroxy functional groups, with the cured coatings having a wide range of desired properties. The ability of 1, 3, 5-triazines with carbamate and isocyanate functional groups to function as efficient crosslinking agents that do not emit formaldehyde, particularly in curable coating compositions, has initiated an intensive search aimed at the discovery of practical and economical processes for its production, a number of which are described in the references incorporated above. While a number of these processes have shown great promise, certain of them also have some disadvantages including, for example, the required use of expensive starting materials and / or the low final output of the desired products. In addition to the processes of the aforementioned references, it has now been surprisingly discovered that acid amides can be prepared with excellent yields or yields by reacting (amino substituted with SI, Ge, or Sn) -1, 3, 5 -triazines, such as melamine silylated with acid halides. It has also been discovered that the use of an acid halide selected from the group consisting of oxalyl chloride, phosgene or phosgene analogues provides excellent yields of 1, 3, 5-triazines with isocyanate functional groups. The 1, 3, 5-triazines with isocyanate functional groups can be further derivatized by contacting them with a wide variety of well-known isocyanate-reactive materials. For example, these isocyanates can be "easily blocked" (e.g., converting the corresponding carbamate) by adding a blocking agent (such as a hydroxyl compound) to 1, 3, 5-triazine with functional groups. isocyanate without isolating it. In addition, isocyanates can be easily oligoed by adding an isocyanate-reactive compound, ultifunctional (eg, a diol or diamine) to 1, 3, 5-triazine with isocyanate functional groups without isolating it. It may be noted that this is known generically to obtain isocyanates by the phosgenation of silylated amines as described by Mironov et al., Zh, Obschei, Khi, L969, 39 (11), 2598-9 and Chem. Abstracts No. 66300r, Vol. 72, 1970, p. 328. However, it is also well known that the amino functionality of amino-1,3,5-triazines, such as melamine, is not equivalent to other types of typical amine functionality. Significantly, melamines are among the least reactive of the "amines" and the most difficult to functionalize, and their behavior can not be correlated normally to that of other known amines. For example, most "typical" amines are highly reactive with acid halides. In a publication of E.M. Smolin and L. Rappaport entitled "S-Triazines and Derivatives", Interscience Publishers Inc., New York, page 333 (1959), it is reported that attempts to react an acid halide with an amino group in a cell were not successful. , 3, 5-triazine such as melamine. In addition, attempts to functionalize amino-1,3,5-triazine frequently result in substitution at the nitrogen in the triazine ring. For example, it is known that the reaction of melamine with alkyl halides, such as allyl chloride, results in the substitution of alkyl on the nitrogen in the triazine ring resulting in isornelamine derivatives.

In fact, it is reported in US Patent No. 3,732,223 that the well-known phosgenation of the amines fails to produce the isocyanate functionality when applied to the amino-1,3,5-triazines. In US Patent No. 3,919,221, thereafter, the phosgenation of amino-1,3,5-triazines having one or two unsubstituted amino groups attached to the triazine ring to obtain monoisocyanate and diisocyanate triazines is reported to occur under certain conditions specific. However, these references do not suggest that the (amino substituted with Si, Ge or Sn) -1, 3, 5-triazines can be reacted with acid halides, such as phosgene, to produce acid amides, and particularly 1, 3, 5-triazines with isocyanate functional groups, in significant yields. Surprisingly, a method has now been discovered in which acid halides, including phosgene (and phosgene sources) and halogenated formates, can be reacted in an easy and effective manner with:. { amino substituted with Si, Ge or Sn) -1, 3, 5-triazines to produce a corresponding acid amine, which includes the 1, 3, 5-t-riazines with isocyanate and carbamate functional groups. In addition, derivatives with isocyanate functional groups can be easily and effectively reacted, in addition with known isocyanate-reactive materials (such as blocking agents) to produce the corresponding isocyanate-based derivatives thereof.

BRIEF DESCRIPTION OF THE INVENTION According to the present invention, there is provided a process for preparing acid amides comprising the step of contacting (a) a substituted amino compound and (b) an acid halide, under reaction conditions sufficient to produce a derivative of corresponding acid amide, characterized in that the substituted amino compound is a (amino substituted with Si, Ge or Sn) 1, 3, 5-triazine represented by Formula (I).

(D where Z and Z1 are independently selected from the group consisting of hydrogen, a hydrocarbyl, a hydrocarbyloxy, a hydrocarbyl, a group represented by the formula -N (Q) 2, and a group represented by the Formula (II). wherein in Formula (II), A is an n-functional support and n is at least 2; each Q is independently selected from the group consisting of hydrogen, hydrocarbyl, hydrocarbyloxy, hydrocarbyl, and M (RX) 3 / with the proviso that at least one Q group is M (Ra) 3 each Z2 is independently selected from a group consisting of hydrogen, a hydrocarbyl, a hydrocarbyloxy, a hydrocarbyl and a group represented by Formula N (Q) 2; each M is independently selected from the group consisting of silicon, germanium and tin; and each R1 is independently selected from alkyl, alkenyl, aryl, aralkyl and alkoxy groups, substituted or unsubstituted.

As indicated above, an acid amide is produced by contacting an acid halide with (amino substituted with Si, Ge or Sn) 1,3,5-triazine. 1, 3, 5-triazine with isocyanate functional groups is produced by using, for example, phosgene, oxalyl chloride or a phosgene analog such as the acid halide. This 1, 3, 5-triazine with isocyanate functional groups can be reacted with isocyanate-reactive materials to produce various isocyanate-based derivatives.

For example, isocyanate groups can be blocked by contacting 1, 3, 5-triazines with isocyanate functional groups with known isocyanate blocking agents, such as certain compounds containing active hydrogen. As another example, the oligomers of the 1, 3, 5-triazines with isocyanate functional groups can be produced by contacting them with the multifunctional, isocyanate-reactive materials, such as diols and diamines. The phrase 1, 3, 5-triazines of "isocyanate and / or isocyanate base", in the context of the present invention, includes trie.zine derivatives having isocyanate functionality, isocyanate-based functionality, or a isocyanate-based and isocyanate-based mixture, for example, when a blocking agent is added in an amount which is less than the molar equivalent of the available isocyanate functionality, then a triazine derivative having both isocyanate and blocked isocyanate functional is procured. If the acid halide employed in the present invention is a hydrocarbyl haloformate, such as alkyl or aryl haloformate, then the resulting acid amide is 1, 3, 5-t;: iazine with carbamate functional groups. When practicing the process in this manner, there is no need to add an isocyanate-reactive material as described above to obtain a 1,3,5-triazine derivative having carbamate functionality. The process of the present invention can also be practiced by preparing the (amino substituted with Si, Ge or Sn) -1, 3, 5-triazine in situ. This is achieved by mixing an amino-1,3,5-triazine and a reactive compound containing silicon, germanium or tin, such as for example chlorotrimethylsilane. together with the acid halide. The process of this invention is advantageous because halogenated amino-1 -3,5-triazine starting materials are not required. Additionally, the yield or production of the acid amide product is increased by employing the compound of (amino substituted with Si, Ge or Sn) -1, 3, 5-triazine compared to the use of an unsubstituted triazine. In addition, (amino substituted with Si, Ge or Sn) -1, 3, 5-t-riazines, such as n-silylated melamine, can be reacted with for example, phosgene, followed by the reaction of the isocyanate with any of a a wide variety of well-known isocyanate-reactive materials to obtain an isocyanate-based 1, 3, 5-triazine without the handling or isolation of the isocyanate triazine product. Alternatively, the (amino substituted with Si, Ge or Sn) -1, 3, 5-triazine can be reacted with an acid halide, such as alkyl haloformate, to directly obtain an acid halide having carbamate functionality. A preferred use of the acid amides, which include the 1, 3, 5-triazines with isocyanate functional groups and various derivatives thereof is as a crosslinking agent with polyfunctional, active hydrogen-containing resins such as acrylic or polyester resins having hydroxy functional groups, to produce curable compositions which have utility in coating, adhesive, molding and other applications. This and other uses are described in several of the previously incorporated references. These and other features and advantages of the present invention will be more readily understood by those skilled in the art from a reading of the following detailed description.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES As indicated above, the present invention is a novel process for preparing acid amides by contacting an (amino substituted with Si, Ge or Sn) -1,3,5-triazine with an acid halide. The term "amino substituted with Si, Ge or Sn" means within the context of this invention that a group containing silicon (Si), germanium (Ge) or tin (Sn) is attached to the amino group of an amino-1,3 , 5-triazir.aa through (Si), (Ge) or (Sn). The process is carried out under reaction conditions, such as temperature, pressure and for a sufficient time, to result in the formation of the corresponding acid amide. The term "acid amide" as used herein includes the reaction products resulting from the combination of the amine group of a (amino substituted with Si, Ge or Sn) -1, 3, 5-triazine with the halide of an acid halide. When the acid halide employed is, for example, a halo formate, the resulting acid amide is a 1,3,5-triazine with carbamate functional groups. On the other hand, if the acid halide employed is phosgene, oxalyl chloride or a phosgene analog, the resulting acid amide is 1, 3, 5-triazine with isocyanate functional groups. When an isocyanate-reactive material such as a well-known isocyanate blocking agent is added subsequent to the formation of 1, 3, 5-triazine with isocyanate functional groups, the corresponding 1, 3, 5-triazine is obtained with the isocyanate-based functionality (blocked isocyanate). The most highly functional derivatives of these 1, 3, 5-triazines with isocyanate functional groups can also be produced by adding a multifunctional isocyanate reactive material subsequent to the formation of 1, 3, 5-triazine with functional groups isocyanate.

The starting materials of (amino substituted with Si, Ge or Sn) -1, 3, 5-triazine The starting materials of (amino substituted with Si, Ge or Sn) -1, 3, 5-triazine, such as tris (trimethylsilyl) elamine, ie, N, N'N "-tris (trimethylsilyl) -2, 4,6-triamino-1,3,5-triazine, and the oligomers thereof, can be easily prepared using standard and well known techniques for silylating, germanizing and / or tinning the amino group (s) of the amino-1, 3, 5-triazines. The term "(amino substituted with Si, Ge or Sn) -1, 3, 5-triazine" in the context of this invention includes a monomeric 1, 3, 5-triazine having at least one and preferably at least two amino groups substituted with Si, Ge or Sn attached to the triazine ring (guanamines and melamine substituted with Si, Ge or Sn), as well as several N-substituted oligomers of the 1, 3, 5-triazines (for example, dimers, trimers) and tetramers) having at least two substituted amino groups are Si, Ge or Sn attached to the triazine rings per molecule. The term "hydrocarbyl" in the context of the present invention, and in the above formula, is a group containing carbon and hydrogen atoms and includes, for example, alkyl, aryl, aralkyl, alkenyl and substituted derivatives thereof. Likewise, the term "hydrocarbylene" (as used subsequently) refers to a divalent hydrocarbyl, such as, for example, alkylene, arylene, alkenylene, and substituted derivatives thereof. Group A in Formula (II) above is an n-functional support which may be, for example, a hydrocarbon residue (eg, a hydrocarbylene group such as a methylene group), a residue of an amino compound, NH, N (hydrocarbyl), O, S, C02, NHC02, CO (NH) 2 and the like. The (amino substituted with Si, Ge or Sn) -1, 3, 5-triazines containing this group A are referred to herein as (amino substituted with Si, Ge or Sn) -1,3,5-oligomeric triazines. As specific examples of this can be mentioned, for example, silylated self-condensation products of melamine-formaldehyde resins, and silylated oligomers produced by the condensation of n-moles of an elamina-formaldehyde resin with one mole of an n-functional polyol, such as trimethylolpropane. However, preferred for use in the present process, are predominantly onomeric (amino substituted with Si, Ge or Sn) -1, 3, 5-triazine materials, which in Formula (I) are those wherein: at least one of Z and Z1 is a group represented by the formula N (Q) 2, and the other is selected from the group consisting of hydrogen, a hydrocarbyl, a hydrocarbyloxy, a hydrocarbyl and a group represented by the Formula - N (Q) 2, more preferably where both Z and Z1 are N (Q) 2, and at least one group Q in each group -N (Q) 2 is M (RX) 3- For each group M (R1) 3 preferably M is silicon and each R1 is independently selected from the group consisting of substituted or unsubstituted alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, aralkyl of 2 to 20 carbon atoms, arylene of 8 to 20 carbon atoms, and alkoxy of 1 to 20 carbon atoms. More preferably, M is silicon and each R is independently selected from the group consisting of alkyl of 1 to 6 carbon atoms, most preferably methyl. Especially preferred for use in the process of this invention is a substantially monomeric N-silylated melamine, wherein both Z and Z1 are N (Q) 2 and at least one Q in each group -N (Q) is SI ( RX) 3. The most monomeric, N-silylated melamine, most preferred is N, N'N "-tris (trimethylsilyl) melamine. As mentioned previously, the starting materials of (amino substituted with Si, Ge or Sn) -1,3,5-triazine of this invention can be prepared by the in situ reaction of an amino-1,3,5-triazine with a reactive compound (Si, Ge or Sn). Useful a-t-ino-l, 3, 5-triazines are fully described in the previously incorporated patents and patent applications set forth herein. The example reactive compounds (Si, Ge or Sn) can be represented by the formula W (M (R1):?) Nr where M and R1 are as previously defined, W is a leaving group and N is at least 1 The preferred leaving groups, represented by W, include hydrogen, halogen, halogenated acetamides and the like. Other possible leaving groups include, for example, anions of other amides, imides, carbamates, sulfonamides, sulfonamides, amines, imidates derived from imidate esters, alkyl, aryl and aralkyl mercaptides, alkyl, aryl and aralkyl sulfonates. , perfluorosulfonates, alkyl, aryl and aralkyl carboxylates, perfluorocarboxylates, azide, cyanide, perhaloalkyl such as trihaloalkoxy, aryloxy, aralkoxy, halogenated derivatives thereof, including perhaloalkoxy such as trichloromethoxy derived from the reaction of silylated melamine with the di (trichloromethyl) carbonate equivalent of phosgene, and the like. It is most preferred that M be silicon. The most preferred reactive compounds (Si, Ge or Sn) include, for example, chlorotrimethylsilane, bis (trimethylsilyl) -triflucroaceta ida, trimethylsilylimidazole, and hexamethyldisilazane.

Acid Halides Examples of acid halides useful in the practice of this invention are fully disclosed in previously incorporated U.S. Patent No. 5,228,865. Preferred acid halides, suitable for use in the practice of this invention, include, for example, hydrocarbyl haloformates such as alkyl chloroformates and aryl chloroformates, acyl chlorides, haloalkylcarbonyl chlorides, acryloyl chlorides, chlorides carbamoyl, alkylene bis chlorides, phosgens and mixtures thereof. The most preferred acid halides are methyl chloroformate, n-butyl chloroformate, n-butyl fluoroformate, phenyl chloroformate, 2-chloroethyl chloroformate, ethyl chloroformate, propyl chloroformate, isopropyl chloroformate, isobutyl chloroformate, 2-ethylhexyl chloroformate, chlorosacetyl chloride, 4-chlorobutyryl chloride, acryloyl chloride, methacryloyl chloride, oxalyl chloride, ethyl oxalyl chloride, benzoyl chloride, para-nitrobenzoyl chloride, acetyl chloride, stearoyl chloride, and phosgene. A particularly preferred acid halide for use in the present invention is phosgene which is well known to those skilled in the art as represented by the formula C1C (0) C1. Phosgene, as defined within the context of this invention, also includes phosgene analogs capable of serving as a source of phosgene, as well as phosgene equivalents which are generally well known to those skilled in the art. Exemplary phosgene analogs include, without limitation, diphosgene and triphosgene. The diphosgene (trichloromethyl chloroformate) and triphosgene (chloromethyl carbonate) are represented, deferentially, by the formulas C1C (0) CC13 and CI3COC (O) OCCI3. Triphosgene is known to those skilled in the art to be a source of phosgene. See, for example, M. J. Coghlan and B.A. Caley, "Trichloromethyl Carbonate as a Practical Phosgene Source" Tetrahedron Letters, Vol. 30, No. 16, p. 2033-2036 (1989). Exemplary phosgene equivalents include, without limitation, N, N '-carbonyldiamidazole and dicyanocarbonyl. The use of phosgene is most preferred in the present invention for the preparation of the 1,3,5-triazines with isocyanate functional groups.

The Reactive Materials with Isocyanate As mentioned above, the 1,3,5-triazines with isocyanate functional groups that are prepared by the processes of this invention can be reacted subsequently with an isocyanate-reactive material such as an active hydrogen-containing compound to form the 1, 3, 5-triazine derivatives based on isocyanate. Suitable for use in the formation of isocyanate-based derivatives are a wide variety of active hydrogen-containing compounds, such as carbamates, and are described in detail in previously incorporated references. For example, the active hydrogen-containing compounds employed in this process include those known to the person skilled in the art having at least a portion of active hydrogen selected from the group consisting of carboxyl, hydroxyl, thiol, sulfonamide, amido, amine. primary, secondary amine, salts thereof and mixtures thereof. Preferred examples are alcohols, phenols, oximes, hydroxamic ethers, lactams and mixtures of the same. As a specific, preferred example, 1, 3, 5-triazine derivatives with carbamate functional groups can be formed by reacting the triazines with isocyanate functional groups with the compounds containing hydroxyl groups. As suitable hydroxyl group-containing compounds, there may be mentioned, for example, straight or branched monohydric or polyhydric alkanes and alkenes, having from 1 to 20 carbon atoms per molecule, cycloalkanols and cycloa] chenols monohydric or polyhydric they have from 3 to 20 carbon atoms in the molecule, and monohydric and polyhydric arylails having from 7 to 20 atoms per molecule. In addition, these alcohols may also have a substituent such as a halogen atom, a cyano group, an alkoxy group, a sulfoxide group, a sulfone group, a carbonyl group, an ester group, an ether group and an amide group. Mixtures of the above are also suitable. Preferred of the above are saturated, unsaturated, cyclic, linear, aliphatic alcohols having from 1 to 8 carbon atoms, as well as mixtures thereof. As specific, preferred examples can be mentioned methane !, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butar.ol, isobutanol, tert-butanol, pentanol, hexanol, cyclohexanol, heptanol, octanol, ethylhexyl alcohol , benzyl alcohol, allyl alcohol, ethylene chlorohydrin, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, ethoxyethanol, hydroxyethoxyethanol, l-methoxy-2-propanol and mixtures thereof. Also suitable are phenols as the compound containing hydroxyl groups. As specific examples may be mentioned phenol, various alkyl phenols, various alkoxy phenols, various halogenated phenols, dihydroxybenzene, 4,4-dihydroxydiphenylmethane, various bisphenols such as biphenol-A, and hydroxynaphthalenes. As preferred examples may be mentioned phenol, 2-methyl-phenol, 3-methyl-phenol, 4-methyl-phenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, catechol, resorcinol, hydrolynone and mixtures thereof. Many of the hydroxyl group-containing compounds, mentioned above, are well-known isocyanate blocking agents. Other well known isocyanate blocking agents are also suitable for use herein, and include, for example, those blocking groups that unblock at relatively low temperatures, for example, below about 125 ° C, such as an oxime of an aldehyde or ketone (for example, methylethyl ketoxime, acetonc.oxime and cyclohexanone oxime), lactam (for example, caprolactam), hydroxy ico acid ester, i-idazole, pyrazole, N-hydroxyamide (e.g. N-hydroxy phthalimide), dimethylamine, or other blocking groups such as those cited in US 4444954, the pertinent porcior.es of which are incorporated by reference herein as if exhibited copletly. For use as a crosslinking agent as described in several of the pre-incorporated referencesThe most preferred for the isocyanate-reactive compound are aliphatic alcohols and ether alcohols having from 1 to 8 carbon atoms, such as methanol, ethanol, isopropanol, propanol, isobutanol, n-butanol, t-butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, 2-ethylhexanol, alkyl alcohol, glycidol, stearyl alcohol, ethoxyethanol and l-methoxy-2-propanol.

Process Conditions In the process of the present invention, the (amino substituted with Si, Ge or Sn) -1, 3, 5-triazine and the acid halide are contacted in a reaction system, under conditions such as temperature and pressure, and for a duration of time sufficient to produce the desired acid amide. The reaction system of the present invention is not limiting, and can be any reaction system, such as a vessel or vessel, that can be subjected to the conditions required to obtain the desired acid amide. The relative amounts of the (amino substituted with Si, Ge or Sn) -1, 3, 5-triazine and the acid halide employed in the process are generally in the range from about 1: 1 to about 1:50, and most preferably in the range from about 1: 3 to about 1: 5, on an equivalent weight basis. The reagents can be mixed in various amounts, but typically at least one equivalent of the acid halide is used per equivalent of (amino substituted with Si, Ge or Sn) -1,3,5-triazira. Preferably, an excess of acid halide is used. The reaction components can be brought into contact with any condition of temperature and pressure that will result in the formation of the acid amide. Preferably, the reaction temperature ranges from about 0 ° C to about 200 ° C, and more preferably from 50 ° C to about 100 ° C. In addition, the reaction of the components is preferably carried out at a pressure in the range from about 1.0 X 105 Pa (0 psig) to about 3.5 X 106 Pa (500 psig), and most preferably from about 1.0 X 105. Pa (0 psig) up to approximately 1.5 X 106 Pa (200 psig), depending on the reaction temperature. At these temperatures and pressures, the reaction has been found to produce the acid amides, which include 1, 3, 5-triazine with isocyanate functional groups, in a time period ranging from about 0.5 hours to about 20 hours. The process can be carried out as a continuous or batch process. It can be carried out by simply mixing in any order, the (amino substituted with Si, Ge or Sn) -1, 3, 5-triazine and the acid halide. Alternatively, as mentioned previously, the reaction can be carried out by mixing an amino-1,3,5-triazine, a reactive compound containing Si, Ge or Sn and the acid halide to form the (substituted amino) with Si, Ge or Sn) -1, 3, 5-triazine in situ. The process can be carried out with or without solvents. If a solvent is employed, preferable solvents include nitrobenzene, chlorobenzene, dichlorobenzene, cyclic ethers, and acyl esters. The reaction process is generally carried out under an atmosphere of an inert gas under substantially moisture-free conditions. This minimizes the decomposition of reagents and products by atmospheric moisture. When the reaction product of the acyl amide is obtained as a solution, the acid amide can be isolated by removing the vola compounds under reduced pressure or by disation. The acid amide can also be isolated by dissolving the product residue in a solvent and precipitating the acid amide upon addition of a solvent in which the acid amide is substantially insoluble. The acid amide product can also be purified by recrystallization, disation or chromatographic techniques well known to those skilled in the art. When 1, 3, 5-triazine with isocyanate functional groups is prepared by the process described above, it can be subsequently reacted with the isocyanate-reactive material described herein and in several of the previously incorporated references. In general, 1, 3, 5-triazine with isocyanate functional groups and the isocyanate-reactive material can be reacted at temperatures ranging from about -20 ° C to about 200 ° C., and during variable times, depending on the material reactive with isocyanate. For the most suitable blocking agents, the components are reacted at temperatures ranging from about 20 ° C to about 40 ° C when the blocking agents are added. This blocking reaction is carried out until substantial termination, in general, for a time ranging from about 10 minutes to about 2 hours. The resulting 1, 3, 5-triazines with isocyanate functional groups, based on isocyanate, can be isolated in any desired manner, such as by filtration and distillation of the solvent. The relative amount of isocyanate blocking agent material added to the 1,3,5-triazide with isocyanate functional groups is generally in the range from about 3 to about 30 equivalents of the isocyanate-reactive functionality per isocyanate group. Preferably, the ratio is in the range from about 3: 1 to about 5: 1 in this equivalent basis. If the amount of the active hydrogen-containing compound added to the reaction is less than the molar equivalent of the available isocyanate functionality, then the resulting 1, 3, 5-triazine will have a mixture of isocyanate and isocyanate-based functionality. When used as a "blocked isocyanate" crosslinking agent, it is preferred to add an amount of the blocking agent which will react to form a 1,3,5-riazine with completely blocked isocyanate functional groups. The following examples are proposed as an illustration of certain preferred embodiments of the invention; and no limitation of the invention is implied.

EXAMPLE 1 Preparation of tris-n-butylcarbamoyl-1,3,5-triazine by phosgenation of silylated melamine and the addition of n-butanol One end of a heavy wall quartz tube, 285 mm long, and 22 mm in diameter was equipped with a Hastelloy C-276 end cap. The other end of the tube was sealed by flame finished on a round bottom. A water condenser 90 mm long and 35 mm in diameter was placed concentrically on the outside of the quartz tube about 40 mm from the closed end. This capacitor was built as follows. Rubber plugs were placed on either end of a section of 35 mm in diameter, and 90 mm in length of glass pipe. This section of glass tubing had water inlet / outlet connections near each end. Each of the rubber plugs has been punched through the center with a single hole 22 mm in diameter through which the quartz tube was pushed, so that the rubber plugs formed a seal between the outside of the tube. quartz and the inside of the condenser envelope. The Hastelloy end cap had a 1/8 NPT threaded connection. This connection was coupled to an electronic register pressure transducer and a stainless steel metering valve, by means of a T. The quartz tube was charged with N, N 'N "-tris (tri-methylsilyl) melamine ( 100 mg). A small Teflon coated magnetic stir bar was placed inside the quartz tube and the tube was held vertically in a bell so that the Hastelloy end cap was on top of the quartz tube reactor. The reaction equipment was attached to a vacuum manifold through the metering valve. A phosgene cylinder was also attached to the vacuum manifold. The reaction tube, the vacuum manifold and the connection tubes were evacuated. An acetone bath with dry ice was placed around the bottom end of the quartz reaction tube. The valve in the vacuum manifold leading to the vacuum pump was closed and the valve in the phosgene cylinder was slowly opened. Approximately 2 mm of phosgene was condensed in the reactor. The phosgene cylinder valve and the reactor valve were closed. The connection lines and the vacuum manifold were flooded with dry hydrogen in a caustic scrubber. The thick suspension of acetone with dry ice was removed from around the end of the reaction tube and the reaction mixture was allowed to warm to ambient temperature. The reactor was disconnected from the vacuum manifold. The reactor was pressurized to 8.4 X 105 Pa (107 psig) with argon. The flow of water through the condenser started. The reaction mixture was heated to reflux by placing the lower end of the reactor in an oil bath at 100 ° C. The reaction mixture was stirred with a magnetic stirrer placed under the oil bath. Stirring and reflux were continued for 17 hours. A white precipitate formed and the pressure in the reaction tube was raised to 9.0 X 105 Pa (116 psig). The reaction mixture was allowed to cool to room temperature. The flow of water through the condenser stopped. The reactor valve was opened and the excess phosgene was released in a caustic scrubber. The Hastelloy layer was temporarily removed and n-butanol (2 mL) was added with stirring. All the precipitate dissolved promptly after the addition of n-butanol. The reactor was opened and the reaction mixture was placed in a round bottom flask. The volatiles were removed from the reaction mixture at room temperature under high vacuum. The remaining white solid residue was analyzed by HPLC and found to be mainly tris-n-butylc-rbamoyl-1,3,5-triazine.

EXAMPLE 2 Preparation of tris-n-butylcarbamoyl-1,3,5-triazine by phosgenation of silylated melamine prepared in situ and addition of n-butanol The reactor described in Example 1 was charged with melamine (100 mg), chlorotrimethylsilane (1 ml) and nitrobenzene (2 L). The reaction mixture was frozen in the acetone slurry and dry ice and the reactor was evacuated. Phosgene (approximately 2 mL) was condensed in the reactor. The reactor was pressurized to 7.9 X 10? Pa (100 psig) with argon. The reaction mixture was stirred magnetically and heated to reflux with an oil bath at 100 ° C. The reaction mixture was maintained under these conditions for 42 hours. The reactor was vented to the caustic scrubber to remove excess phosgene. The reactor was then cooled to room temperature and the excess chlorotri ethylsilane was distilled from the reactor under vacuum. The Hastelloy cap was temporarily removed and n-butanol (2 mL) was added. This mixture was stirred briefly, the reactor was opened and the reaction mixture was filtered to remove unreacted melamine. The volatile components were removed from the filtrate, giving 15 mg of the solid residue. This residue was analyzed by HPLC and found to be mainly tris-n-butylcarbamoyl-1,3,5-triazine.

EXAMPLE 3 Preparation of Tris-n-butylcarbamoyl-1,3,5-triazine by phosgenation of melamine in the presence of bis (trimethylsilyl) trifluoroacetamide and the addition of n-butanol.

The reactor described in Example 1 was charged with melamine (100 mg), bis (trimethylsilyl) trifluoroacetamide (1 mL), and nitrobenzene (2 mL). The reaction mixture was frozen in the slurry of acetone with dry ice and the reactor was evacuated. The oxygen (approximately 2 L) was condensed in the reactor. The reactor was pressurized to 1.1 X 10fe Pa (150 psig) with argon. The reaction mixture was stirred magnetically and refluxed with an oil bath at 115 ° C. The reaction mixture was kept under these conditions for 1.5 hours. The oil bath was decreased and the excess phosgene was released to a caustic scrubber. The reactor was placed under vacuum to remove the more volatile components of the reaction mixture. The oil bath at 115 ° C was raised and the reaction mixture was heated with stirring for 20 min. The Hastelloy lid was temporarily removed and n-butanol (2 L) was added. Stirring and heating were continued for 15 min. The reactor was cooled, opened and the reaction mixture was filtered. The volatile components were removed under vacuum at room temperature to give 161 mg of the solid residue. This residue was analyzed by HPLC and found to be mainly tris-n-butylcarbamoyl-1,3,5-triazine.

EXAMPLE 4 Preparation of tris-n-butylcabamoyl-1,3,5-triazine by reacting oxalyl chloride with silylated melamine and adding n-butanol N, N ', N "-tris (tri-methyl-yl) melamine (600 mg) and oxalyl chloride (5 L) were placed in a 25 mL round bottom flask equipped with a condenser reflux and a magnetic stirrer. This slurry was stirred under reflux for 18 hours under nitrogen atmosphere. A sample of the reaction mixture gave a very strong isocyanate band at 2240 cm "1 in the infrared spectrum.The volatile components of the reaction mixture were distilled from the reaction mixture at room temperature under high vacuum. dissolved in n-butanol.The main product in this solution was tris-n-butylcé.rbamoyl-1,3,5-triazine as determined by HPLC analysis.

EXAMPLE 5 Preparation of tris-n-butylcarbamoyl-1,3,5-triazine from silylated melamine and n-butyl chloroformate N, N'N "-tris (trimethylsilyl) elaine (600 mg) and n-butyl chloroformate (5 ml) were placed in a 25 mL round bottom flask of 14/20 equipped with a reflux condenser and a magnetic stirrer The reaction flask was placed in an oil bath at 90 ° C and stirred magnetically for 18 hours under a nitrogen atmosphere. A portion of the reaction mixture was rapidly cooled with n-butanol to destroy the unreacted starting reagents and analyzed by HPLC. The HPLC trace showed the presence of tris-n-butylcarbamoyl-1,3,5-triazine.

EXAMPLE 6 Preparation of a mixture of mono, bis and tris-n-butylcarbamoyl-1,3,5-triazine from silylated melamine and n-butyl fluoroformate A slurry of n-butyl chloroformate (10 g) and sodium fluoride (6 g) in anhydrous acetonitrile (40 mL) was refluxed overnight with magnetic stirring under an argon atmosphere. The reaction mixture was cooled to room temperature and the supernatant was decanted from the solids; This supernatant was analyzed by VPC and found to be primarily a solution of n-butyl fluoroformate in acetonitrile. This solution (2 mL) was mixed with N, N ', N "-tris (trimethylsilyl) elamine (100 mg) in a small round bottom flask under an argon atmosphere. The N, N 'N "-tris (trimethylsilyl) elamine was dissolved giving a homogeneous solution. This mixture was heated gently with a heat gun and a white precipitate formed immediately. The volatile components of the reaction mixture were stirred at room temperature under high vacuum.

The remaining white solids were analyzed by FAB MS and found to be a mixture of mono-, bis-, and tris-n-butylcarbamoyl-1, 3,5-triazine. Other variations and modifications of this invention will be obvious to those skilled in the art. This invention is not limited except as set forth in the following claims.

It is noted that in relation to this date, the best method known by the applicant to carry out the present invention is that which is clear from the present description of the invention. Having described the invention as above, the content of the following is claimed as property:

Claims (23)

1. A process for preparing acid amides comprising the step of contacting (a) a substituted amino compound and (b) an acid halide, under reaction conditions sufficient to produce a corresponding acid amide derivative, characterized in that the substituted amino group is a (amino substituted with Si, Ge or Sn) -1, 3, 5-triazine represented by Formula (I): wherein Z and Z1 are independently selected from the group consisting of hydrogen, a hydrocarair, a hydrocarbyloxy, a hydrocarbyl, a group represented by the formula -N (Q) 2, and a group represented by Formula (II). n-i wherein in Formula (II), A is an n-functional support and n is at least 2; each Q is independently selected from the group consisting of hydrogen, hydrocarbyl, hydrocarbyloxy hydrocarbyl, and M (RX) 3 / with the proviso that at least one group Q is M (R1) 3 each Z2 is independently selected from a group consisting of hydrogen, a hydrocarbyl, a hydrocarbyloxy, hydrocarbyl, and a group represented by Formula N (Q) 2; each M is independently selected from the group consisting of silicon, ger anion and tin; and each R1 is independently selected from alkyl / alkenyl, aryl, aralkyl and alkoxy groups, substituted or unsubstituted.

2. The process according to claim 1, characterized in that the acid halide ee is selected from the group consisting of hydrocarbyl haloformates, acyl chlorides, haloalkylcarbonyl chlorides, acryloyl chlorides, carbamoyl chlorides, alkylene bis chlorides, and , arylene bis-chlorides, alkylene bis-chloroformates, phosgens and mixtures thereof.

3. A process according to claim 1, characterized in that the acid halide is selected from the group consisting of methylchloroformate, n-butyl chloroformate, fluoro-n-propyl fluoride, phenyl chloroformate. 2-chloroethyl chloroformate, ethyl chloroformate, propyl chloroformate, isopropyl chloroformate, isobutyl chloroformate, 2-ethylhexyl chloroformate, chloroacetyl chloride, 4-chlorobutyryl chloride, acryl chloride:., ethacryloyl chloride, chloride of oxalyl, acetyl chloride, ethyl oxalyl chloride, stea-raylium chloride, ph? spae and mixtures thereof.

4. The process according to claim 1, characterized in that the acid halide is selected from the group consisting of oxalyl chloride, phosgene / phosgene analogues and mixtures thereof.

5. The process according to claim A, characterized in that it further comprises the step of contacting the reaction product of the (amino substituted with Si, Ge or Sn) -1, -3,5-triazine and the acid halide with an isocyanate-reactive material at a temperature, pressure and for a sufficient length of time to form an isocyanate-based 1,3,5-triazine derivative.

6. The process according to claim 1, characterized in that the acid halide is a hydrocarbyl haloformate.

7. The process according to claim 1, characterized in that the acid halide is selected from the group consisting of alkyl chloroformate and aryl chloroformate.

8. The process according to any of claims 1-7, characterized in that at least one year of Z and Z1 is N (Q) / and the other is selected from the group consisting of hydrogen, a hydrocarbyl, a hydrocarbyloxy, a hydrocarbyl , and a group represented by the formula N (Q) 2.

9. The process according to claim 8, characterized in that both Z and Z1 are N (Q) 2.

10. The process according to claim 9, characterized in that each Q is independently selected from the group consisting of hydrogen and M (R1) 3.

11. The process according to claim 8, characterized in that Z1 is selected from the group consisting of hydrogen and a hydrocarbyl.c

12. The process according to claim 11, characterized in that Z1 is a hydrocarbyl selected from the group consisting of an alkyl of 1 to 20 carbon atoms, an alkenyl of 3 to 20 carbon atoms, an aryl of 6 to 20 atoms of carbon, and an aralkyl of 7 to 20 carbon atoms.

13. The process according to any of claims 1-7, characterized in that M is silicon.

14. The process according to claims 1-7, characterized in that each R1 is independently selected from the group consisting of substituted or unsubstituted alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 20 carbon atoms, 6 to 20 carbon atoms, aralkyl of 2 to 20 carbon atoms, arylene of 8 to 20 carbon atoms, and alkoxy of 1 to 20 carbon atoms.

15. The process according to claim 14, characterized in that each R1 is independently selected from the group consisting of an alkyl of 1 to 6 carbon atoms.

16. The process according to claim 15, characterized in that R1 is methyl.

17. The process according to any of claims 1-7, characterized in that the (amino substituted with Si, Ge or Sn) -1, 3, 5-triazine and the acid halide are contacted in an amount ranging from about 1: 1 to about 1:50 on a weight basis of equivalent.

18. The process according to any of claims 1-7, characterized in that the (amino substituted with Si, Ge or Sn) - 1, 3, 5-triazine and the acid halide are contacted at a temperature ranging from ca. 0 ° C to about 200 ° C and a pressure ranging from about 1.0 X 105 Pa (0 psig) to about 3.5 X 106 Pa (500 psig).

19. The process according to any of claims 1-7, characterized in that the. { amino substituted with Si, Ge or Sn) -1 / 3, 5-triazine and the acid halide are contacted under an inert gas atmosphere under substantially moisture-free conditions.

20. The process according to any of claims 1-7, characterized in that M is silicon and each R1 is independently selected from the group consisting of an alkyl of 1 to 6 carbon atoms.

21. The process according to claim 8, characterized in that M is silicon and each R1 is independently selected from the group consisting of an alkyl of 1 to 6 carbon atoms.

22. The process according to any of claims 1-7, characterized in that the (amino substituted with Si, Ge or Sn) - L, 3, 5-triazine and the acid halide are contacted in an amount that varies from about 1: 1 to about 1:50 on a weight basis equivalent, at a temperature ranging from about 0 ° C to about 200 ° C, at a pressure ranging from about 1.0 X 105 Pa (0 psig) to about 3.5 X 106 Pa (500 psig), and under an atmosphere of an inert gas under substantially free moisture conditions.

23. The process according to claim 8, characterized in that the (amino substituted with Si, Ge or Sn) -1, 3, 5-triazine and the acid halide are contacted in an amount ranging from about 1: 1 to about 1:50 on a weight basis equivalent, at a temperature ranging from about 0 ° C to about 200 ° C, at a pressure ranging from about 1.0 X 105 Pa (0 psig) to about 3.5 X 106 Pa (500 psig), and under an atmosphere of an inert gas under substantially moisture-free conditions.