AU3978999A - Creación de Inventos y Patentes con Inteligencia Artificial

AU3978999A – Process for the preparation of triazine carbamates
– Google Patents

AU3978999A – Process for the preparation of triazine carbamates
– Google Patents
Process for the preparation of triazine carbamates

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Publication number
AU3978999A

AU3978999A
AU39789/99A
AU3978999A
AU3978999A
AU 3978999 A
AU3978999 A
AU 3978999A
AU 39789/99 A
AU39789/99 A
AU 39789/99A
AU 3978999 A
AU3978999 A
AU 3978999A
AU 3978999 A
AU3978999 A
AU 3978999A
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AU
Australia
Prior art keywords
group
isocyanate
triazine
dimethyl
alcohol
Prior art date
1998-06-16
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)

Abandoned

Application number
AU39789/99A
Inventor
Hong Zhao
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Cytec Technology Corp

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Cytec Technology Corp
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1998-06-16
Filing date
1999-05-10
Publication date
2000-01-05

1999-05-10
Application filed by Cytec Technology Corp
filed
Critical
Cytec Technology Corp

2000-01-05
Publication of AU3978999A
publication
Critical
patent/AU3978999A/en

Status
Abandoned
legal-status
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Classifications

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07D—HETEROCYCLIC COMPOUNDS

C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings

C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings

C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members

C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms

C07D251/40—Nitrogen atoms

C07D251/54—Three nitrogen atoms

C07D251/70—Other substituted melamines

Description

WO 99/65883 PCT/US99/10182 PROCESS FOR THE PREPARATION OF TRIAZINE CARBAMATES 5 BACKGROUND OF THE INVENTION Field of the Invention This invention relates to the preparation of 1,3,5-triazine carbamates which are 10 suitable for use as crosslinking agents in curable compositions, particularly in coating compositions capable of curing at relatively low temperatures without releasing formaldehyde during cure. Description of the Related Art 15 Various derivatives of amino- 1,3,5-triazines are described in the literature as being utilized in a wide variety of fields. An important use of certain of these derivatives, such as the methoxymethyl derivatives of melamine and guanamine, is as crosslinkers and /or reactive modifiers in curable compositions which contain resins having active hydrogen groups. While these methoxymethyl derivatives provide excellent results in a number of aspects, they also 20 have the disadvantage of releasing formaldehyde as a volatile by-product under curing conditions. It has long been a desire of industry to find acceptable alternatives which do not emit formaldehyde during cure. One such non-formaldehyde alternative that has shown great promise is the class of isocyanate and carbamate-functional 1,3,5-triazine crosslinking agents disclosed in commonly 25 owned U.S. Pat. Nos. 4,939,213, 5,084,541 and 5,288,865, EP-A-0604922 (corresponding to United States Application Serial No. 07/998,313, filed December 29, 1992), EP-A-0624577 (corresponding to United States Application Serial No. 08/061,905, filed May 14, 1993), United States Application Serial No. 08/138,581 (filed October 15, 1993), United States Application Serial No. 08/239,009 (filed May 6, 1994), United States Application Serial No. 08/286,835 30 (filed August 5, 1994), United States Application Serial No. 08/324,549 (filed October 18, 1994) and United States Application Serial No. 08/08/705,472 (filed August 29, 1996), which are incorporated by reference herein for all purposes as if fully set forth. Specifically, the carbamate functional 1,3,5-triazines disclosed in these references have been found to be particularly useful as crosslinkers in coating compositions based upon hydroxy functional 35 resins, with the cured coatings possessing a wide range of desirable properties. Other non-formaldehyde emitting alternatives include, for example, the class of lactam substituted 1,3,5-triazine crosslinking agents disclosed in commonly owned WO 93/10117 (corresponding to United States Application Serial No. 07/973,676, filed November 9, 1992) 1 WO 99/65883 PCTIUS99/10182 and the class of acetal and enamine functional 1,3,5-triazine crosslinking agents disclosed in commonly owned United States Application Serial No. 08/408,323 (filed March 21, 1995), which are also incorporated by reference herein for all purposes as if fully set forth. While some of these these non-formaldehyde emitting systems have shown great 5 promise, their preparation methods can be somewhat cumbersome, difficult and expensive. For example, in previously incorporated US 4,939,213 and US 5,084,541, the 1,3,5-triazine carbamates are produced in a two-step process by first reacting an amino- 1,3,5-triazine with oxalyl chloride to produce an isocyanate functional intermediate, then reacting this intermediate with an alcohol. Further, in previously incorporated US 5,288,865, carbamate 10 functional 1,3,5-triazines are produced in a one-step process by reacting a haloamino-1,3,5 triazine with an acid halide. The primary disadvantage of these processes include the use of certain costly halogenated starting materials, production of substantial amounts of halogenated by-products, and low ultimate yield of the desired products. Therefore, the search continues for simple and economical routes to preparing non-formaldehyde 15 crosslinkers. Some of the problems with these processes have been solved by the process disclosed in previously incorporated United States Application Ser. No. 08/061,905, wherein carbamate functional 1,3,5-triazines are produced by reacting an at least bis-amino 1,3,5 triazine with an acyclic organic carbonate in the presence of a strong base. Disadavantages 20 to this process include, for example, that the strong base must be neutralized to remove it from the end product and that certain aspects of the reaction must be carefully controlled in order to avoid color in the end product. In regard to the production of mono-carbamates, Matsui and Otaguro, 1976, Kogyo Kagaku Zasshi, 6Z: 12, pp. 2402-2403 describe the formation of a mono-substituted product, 25 2-(ethoxycarbonylamino)-4,6-dichloro-1,3,5-triazine, from the reaction of cyanuric chloride with potassium cyanate. However, the attainment of di-substituted derivatives are not therein disclosed. It has now been surprisingly discovered that di- and more highly substituted 1,3,5 triazine carbamate crosslinkers can be produced by reacting, in an organic solvent reaction 30 medium, (i) a 1,3,5-triazine derivative having thereon at least two cyanate displacable leaving groups and (ii) a cyanate-containing reagent, in the presence of (iii) an isocyanate-reactive compound, such as a hydroxy-functional compound. The process of the present invention advantageously does not require any costly starting materials. Furthermore, the 1,3,5-triazine carbamate crosslinkers prepared by the present invention’s process can be produced directly, 5 without handling of the 1,3,5-triazine intermediates. When employed in coating compositions, the 1,3,5-triazine carbamate crosslinkers produced by the present invention’s process 2 WO 99/65883 PCTIUS99/10182 produce films which have good appearance, solvent resistance and gloss characteristics. SUMMARY OF THE INVENTION 5 In accordance with the present invention, there is provided a process for preparing a 1,3,5-triazine carbamate derivative having the formula (1) or an oligomer thereof: R 10 NQN
R
1 00CNH N NHCOOR 2 15 wherein R is selected from the group consisting of -NHCOOR’, hydrogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio, amido, sulfonamido, amino and a leaving group; and wherein R 1 , R 2 or R 3 is, independently, a hydrocarbyl or a hydrocarbyloxyhydrocarbyl, said process comprising the step of contacting: 20 (i) a 1,3,5-triazine derivative having at least two cyanate-displaceable leaving groups represented by the formula (II) or an oligomer thereof: L2 25 N N L1 N L 3 wherein L’ is selected from the group consisting of hydrogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio, amido, sulfonamido, amino and a leaving group ; and wherein each of L 2 and L 3 is, independently, a leaving group; 5 (ii) a cyanate-group containing reagent capable of reaction therewith; (iii) an isocyanate-reactive compound; and 3 WO 99/65883 PCT/US99/10182 (iv) an isocyanate-unreactive organic solvent, wherein said contacting is carried out at a temperature and length of time sufficient to produce a 1,3,5-triazine carbamate derivative having at least two carbamate groups, with the proviso that if the organic solvent is not sufficiently polar to produce a bis-carbamate derivative, contacting is carried out in the 5 presence of a phase-transfer catalyst. An important use of the 1,3,5-triazine carbamates produced by the novel process of the present invention is based on their ability to act as crosslinking agents in curable compositions, and especially those curable compositions which contain polyfunctional materials which have active hydrogen groups. The 1,3,5-triazine carbamates of the present 10 invention therefore find use, for example, in coatings, adhesives and molding applications. As indicated above, the advantages of the present process include, for example: (1) the present process does not require the use of environmentally undesirable formaldehyde; (2) the present process does not require the use of costly halogentated reagents such as 15 oxalyl chloride; and (3) the present process does not require the handling or isolation of an isocyanate intermediate. These and other features and advantages of the present invention will be more readily understood by those of ordinary skill in the art from a reading of the following detailed 20 description. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 25 As mentioned above, the present invention is a novel process for preparing 1,3,5 triazine carbamate derivatives having at least two carbamate groups. The term «hydrocarbyl» broadly refers to a group which contains at least carbon and hydrogen atoms and includes, for example, alkyl, aryl, aralkyl, alkenyl, and substituted derivatives thereof. 30 The term «amido» includes, for example, both substituted and unsubstituted amidos, such as alkyl and /or aryl substituted amido groups. The term «amino» includes cyclic and non-cyclic amino. For example, the term includes amino, alkyl and/or aryl substituted aminos and heterocyclic N-containing groups optionally containing a different heteroatom in the ring structure. As examples of non-cyclic 35 amino groups may be mentioned an amino group, a monoalkylamino, a monoaralkylamino, a monoarylamino, a dialkylamino, a diaralkylamino and a diarylamino. As examples of cyclic 4 WO 99/65883 PCT/US99/10182 amino groups may be mentioned substituted and unsubstituted pyrrolidino, azepino, piperizino and morpholino groups. The term «leaving group» means a group which can be displaced by a cyanate compound. 5 The term «polar organic solvent» in the context of the present invention refers to any solvent having a dipole moment of at least 3.0 Deby Units and includes solvents such as amides, phosphorus-containing compounds, sulfones, sulfoxides, nitriles, carbonates, lactones, nitro compounds, diketones, keto alcohols, and mixtures thereof. Polar organic solvents having a dipole moment of at least 3.0 Deby Units are discussed in detail in U.S. Pat. 10 No. 5,233,003, the contents of which are hereby incorporated by reference herein for all purposes as if fully set forth. The term «non-polar organic solvent» in the context of the present invention refers to any solvent which has a dipole moment of less than 3.0 Deby Units and includes solvents such as ketones, ethers, esters, hydrocarbons, halocarbons and mixtures thereof. 15 The 1,3.5-Triazine Starting Material i) The 1,3,5-triazine (i) suitable for use in the present invention’s process is represented by the formula (II) or an oligomer thereof: 20 L2 L1 N L3 25 wherein Ll is selected from the group consisting of hydrogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio, amido, sulfonamido, amino and a leaving group ; and 30 wherein each of L 2 and L 3 is, independently, a leaving group. Examples of suitable leaving groups include those which are displaceable by cyanate, for example, halogens, tertiary amines and sulfonates. In a preferred embodiment, groups
L
1 , L 2 and L 3 of the 1,3,5-triazine starting material are all, independently, a halogen, more preferably groups L’, L 2 and L 3 are chloride, corresponding to cyanuric chloride. 35 5 WO 99/65883 PCT/US99/10182 Cyanate-Group Containing Reagent Capable of Reacting with the 1.3,5-Triazine (ii) Component (ii) is a cyanate-group containing reagent capable of supplying at least one cyanate group for reaction with the 1,3,5-triazine (i). In a preferred embodiment, the cyanate group containing reagent is represented by the formula: 5 W(NCO)n wherein n is at least 1 and W is an n-functional moiety selected from the group consisting of metal, hydrogen, ammonium, phosphonium, sulfonium, silyl and mixtures thereof. 10 More preferably, the n-functional moiety, W, is selected from the group consisting of sodium, potassium, quaternary ammonium such as tetraalkylammonium and arylltrialkylammonium, quaternary phosphonium such as methyl triphenylphosphonium and mixtures thereof. 15 Isocyanate-Reactive Compound (iii) Component (iii) is an isocyanate-reactive compound capable of reacting with a 1,3,5 triazine isocyanate intermediate to produce a 1,3,5-triazine carbamate. Isocyanate-reactive compounds are well-known in the art and include hydroxy compounds, amines, and mercaptans. Other suitable isocyanate-reactive compounds for use herein include those 20 blocking groups which deblock at relatively low temperatures, e.g., below about 125″C, such as an oxime of an aldehyde or ketone (e.g., methylethyl-ketoxime, acetone oxime and cyclohexanone oxime), N-hydroxyimide (e.g., N-hydroxyphthalimide) and other blocking groups such as those recited in U.S. Pat. No. 4,444,954, the pertinent portions of which are incorporated by reference herein as if fully set forth. Thus, more highly functional oligomeric 25 derivatives of isocyanate functional 1,3,5-triazine intermediates can be produced by including a multifunctional isocyanate-reactive compound. A wide variety of isocyanate-reactive materials are suitable for use in forming the carbamates and are described in detail in the previously incorporated references. Especially suitable examples of the isocyanate-reactive material useable in forming carbamates are the 30 hydroxy functional compounds, including alcohols, phenols, oximes, hydroxamic ethers, and mixtures thereof. As preferred examples may be mentioned alcohols and phenols, with alcohols being particularly preferred. As suitable alcohols may be mentioned straight or branched monohydric or polyhydric alkanols and alkenols having 1 to 20 carbon atoms per molecule, monohydric or polyhydric 35 cycloalkanols and cycloalkenols having 3 to 20 carbon atoms in the molecule, and monohydric and polyhydric arylalkyls having 7 to 20 carbon atoms per molecule. Further, these alcohols 6 WO 99/65883 PCT/US99/10182 may also have a substituent such as a halogen atom, a cyano group, an alkoxy group, a sulfone group, a carbonyl group, an ester group, an ether group and an amide group. Mixtures of the above are also suitable. As preferred alcohols may be mentioned aliphatic linear, cyclic, saturated, or 5 unsaturated alcohols having 1 to 8 carbon atoms, as well as mixtures thereof. As specific preferred examples may be mentioned methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, 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, 1 10 methoxy-2-propanol and mixtures thereof. As suitable phenols may be mentioned alkyl phenols, alkoxy phenols, halogenated phenols, dihydroxybenzene, 4,4-dihydroxydiphenylmethane, various bisphenols such as bisphenol-A, and hydroxynaphthalenes. Specifically preferred phenols include phenol, 2 methyl phenol, 3-methyl phenol, 4-methyl phenol, 2-chlorophenol, 3-chlorophenol, 4 15 chlorophenol, catechol, resorcinol, hydroquinone, and mixtures thereof. A carbamate functional 1,3,5-triazine derivative can readily be produced by adding the isocyanate-reactive compound prior to formation of the isocyanate functional 1,3,5-triazine intermediate or subsequent to the formation of the isocyanate intermediate. A first preferred embodiment of the process of the present invention is to contact components (i), (ii), and (iii) 20 simultaneously in the presence of an organic solvent to produce a 1,3,5-triazine carbamate. A second preferred embodiment of the novel process is to first contact components (i) and (ii) in the presence of an organic solvent, thereby forming an isocyanate functional 1,3,5-triazine intermediate and, thereafter, add component (iii), for example, a hydroxy compound, to produce a 1,3,5-triazine carbamate. 25 The Organic Solvent (iv) In the process of the present invention, contacting is carried out in an organic solvent reaction medium. The reaction medium preferably used in the present invention is an organic solvent which is substantially non-reactive with isocyanates i.e., an isocyanate-unreactive 30 organic solvent. If an hydroxy compound is employed as the isocyanate-reactive component (iii), the reaction medium may comprise a mixture of (a) the organic solvent and (b) hydroxy compound (iii), which, in this instance, may serve as isocyanate-reactive component (i.e. a reactant) and co-solvent. In this mixture, the organic solvent is preferably an isocyanate-unreactive organic 35 solvent. The preferred isocyanate-reactive components which may be used as co-solvent include alcohols having 1 to 20 carbon atoms per molecule, including, for example, alcohols 7 WO 99/65883 PCT/US99/10182 such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, 2-ethyl hexanol, alkyl alcohol, glycidol, stearyl alcohol, ethoxyethanol, 1-methoxy-2-propanol, isomers thereof, and mixtures thereof. Solvents having a plurality of functionalities such as ethylene glycol monomethyl ether, methoxypropyl acetate, and the like 5 and mixed solvents are also usable. Isocyanate-unreactive organic solvents which may be used in the present invention include isocyanate-unreactive polar solvents, isocyanate-unreactive non-polar solvents and mixtures thereof. Isocyanate-unreactive polar solvents are preferred. Examples of suitable isocyanate-unreactive polar solvents include amides such as 10 N,N-dimethyl acetamide, N-methyl pyrrolidone, N,N-dimethyl formamide, phosphorus containing compounds such as hexamethyl phosphoramide (HMPA) and hexamethyl phosphorus triamide (HMPT), sulfones such as dimethyl sulfone, sulfolane, sulfoxides such as dimethyl sulfoxide, nitriles such as acetonitrile, propionitrile, benzonitrile, carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, 15 lactones such as butyrolactone, propiolactone, nitro compounds such as nitromethane, nitroethane, nitropropane, nitrobenzene, diketones such as acetyl acetone, keto alcohols such as diacetone alcohol, and mixtures thereof. The preferred isocyanate-unreactive polar solvent is N,N-dimethyl acetamide. Examples of suitable isocyanate-unreactive non-polar solvents include esters such as 20 methyl acetate, ethyl acetate, ethyl formate, methoxypropyl acetate, ketones such as acetone, methyl ethyl ketone, methyl iso-propyl ketone, methyl iso-butyl ketone, cyclohexanone, ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, hydrocarbons such as benzene, toluene, ethyl benzene, xylene, mesitylene, hexane, heptane, cyclohexane, halocarbons such as methylene chloride, chlorobenzene, 25 1,1,1-trichloroethane, and mixtures thereof. The Novel Process The novel process of the invention comprises contacting a 1,3,5-triazine derivative of the formula 11, above, a cyanate-group-containing reagent, an isocyanate-reactive compound 30 and an organic solvent at a temperature and for a length of time sufficient to produce a 1,3,5 triazine carbamate derivative having at least two carbamate groups. As described above, the organic solvent (i.e., reaction medium) is preferably an isocyanate unreactive organic solvent. Importantly, the isocyanate-unreactive organic solvent employed in the present invention’s process must be sufficiently polar to produce an at least bis-carbamate derivative. Preferably, 35 the organic solvent has a dipole moment of at least 3.0 Deby Units. Although a phase transfer catalyst may be used with a sufficiently polar organic solvent to augment the level of 8 WO 99/65883 PCTIUS99/10182 substitution and/or reaction rates, it is not required. However, when a non-polar organic solvent is used as the reaction medium, a phase transfer catalyst must be employed. Further, if the organic solvent is polar, however, not sufficiently polar to produce an at least bis carbamate derivative, a phase transfer catalyst should also be employed to attain the desired 5 bis-carbamate derivative. Examples of suitable phase transfer catalysts include quaternary salts, crown ethers, and other metal chelating agents. As examples of quaternary salts may be mentioned quaternary ammonium salts, quaternary phosphonium salts and sulfonium salts. Quaternary ammonium salts such as quaternary ammonium halides and cyanates are preferred. Benzyl 10 trialkylammonium chloride, benzyl trialkylammonium bromide, and benzyl trialkylammonium cyanate are especially preferred. Without being bound by any particular theory, it is believed that the attainment of highly substituted products is dependent on the solubility of the cyanate-group containing reagent (iv) in the reaction medium. That is, for the reaction to proceed at a rate sufficient to produce 15 highly substituted products such as bis- and tris-substituted products, the cyanate group containing reagent and reaction medium (i.e., organic solvent) should be chosen in such a manner as to result in a sufficient concentration of the cyanate-group containing reagent in the reaction mixture. Thus, when an organic cyanate-group containing reagent such as a quaternary ammonium cyanate is used, solvents of low to moderate polarity can be used in 20 the present process to produce highly substituted products because of the substantial solubility of such reagents in solvents of low polarity. If, on the other hand, an inorganic cyanate group-containing reagent such as sodium or potassium cyanate is used, a solvent of high polarity capable of dissolving such reagents must be used to result in a sufficient concentration of the cyanate-group containg reagent in the reaction mixture, thereby allowing 25 for the production of more highly substituted products (i.e. the bis- and tris-carbamates). Alternatively, if a solvent of low polarity is used with an inorganic-cyanate group containing reagent such as sodium or potassium, a phase transfer catalyst may be needed in the reaction mixture to promote the solubility of the metal cyanate in the low-polar organic solvent, thereby producing sufficient concentrations of an at least bis-carbamate derivative. Whenever 30 a non-polar organic solvent is employed as the reaction medium, a phase transfer catalyst must be present in the reaction mixture, which catalyst, it is believed, serves to promote the solubility of the cyanate-group containing reagent in the non-polar solvent allowing for the production of at least bis-carbamate derivatives. Contacting may be advantageously carried out in the presence of a catalyst which is 35 substantially non-reactive with component (i), for promoting rapid reaction including, for example, phase transfer catalysts, basic catalysts, and organometallic catalysts. 9 WO 99/65883 PCTIUS99/10182 As examples of basic catalysts may be mentioned strong nitrogenous bases such as amines, imines, amidines and guanidines and inorganic bases such as alkali metal salts. Suitable amines include tertiary amines, including trialkyl amines, triaryl amines, alkyl diaryl amines, dialkyl aryl amines, cyclic amines, bicyclic amines, polycyclic amines, heteroaromatic 5 amines and mixtures thereof, including heteroaromatic amines such as 4-pyrrolidinopyridine, 4-piperidiropyridine, and 4-morpholinopyridine and bicyclic amines such as 1,4-diaza-(2.2.2) bicyclooctane (DABCO). Of the basic catalysts, 1,4-diaza-(2.2.2)-bicyclooctane (DABCO) and alkylated guanidines such as tetramethylguanidine are preferred. Suitable examples of organometallic catalysts include organotin compounds such as 10 dibutyltin di-2-ethylhexoate, dibutyltin diisooctyl maleate, dibenzyltin di-2-ethylhexoate, dibutyltin dilaurate, dimethyltin dilaurate (UL-28), tetrabutyl diacetoxy distannoxane (TK-1), tetramethyl diacetoxy distannoxane, tetrapropyl diacetoxy distannoxane, dibutyltin dichloride, and the like. The molar ratio of cyanate to cyanate-reactive functionality employed in the process 15 of the invention is preferably in the range of from about 10:1 corresponding to a 1000% molar excess quantities to about 1:1 which corresponds to molar equivalent quantities. Preferably, the ratio is in the range of from about 5:1 to about 1:1. In the process of the present invention, the reaction ingredients are contacted in a suitable reactor at a temperature and length of time sufficient to produce the desired 1,3,5 20 triazine carbamate The process may be carried out in any reactor system such as a vessel or container which can be subject to the conditions required to obtain the desired 1,3,5 triazine carbamates. The reaction components are preferably contacted at a temperature at which the reaction of cyanate groups, on the cyanate-group containing reagent, with the leaving groups 25 on the 1,3,5-triazine derivative proceed at a convenient rate to produce a 1,3,5-triazine carbamate. The reaction of the components is preferably conducted at atmospheric pressure, however, super atmospheric pressures may also be employed, particularly when substantially volatile isocyanate reactive materials are present in the reaction mixture. Preferably, the reaction temperature ranges from about 250C to about 1600C, and more preferably from 30 about 80 0 C to about 1200C. Under these conditions, the reaction can produce 1,3,5-triazine carbamates within a period of time typically ranging from about 1 hour to about 24 hours. Since carbamate functional 1,3,5-triazines are the desired product in the present process, the amount of isocyanate reactive compound, i.e., hydroxy compound, will typically be a stoichiometric excess (based upon isocyanate formation). The molar ratio of the 35 isocyanate-reactive functionality added to the isocyanate functionality is generally in the range of from about 10:1 to about 1:1 on the basis of equivalents of isocyanate-reactive functionality 10 WO 99/65883 PCT/US99/10182 per isocyanate group. Preferably, the ratio is in the range of about 3:1 to about 1:1 on such equivalent basis. The examples which follow are intended as an illustration of certain preferred embodiments of the invention, and no limitation of the invention is implied. NMR spectra were 5 obtained on a Varian Unity 300 Plus. IR spectrum was obtained on a Digilab FTS 60A with 16 scans (Resolution 4). MSEI was conducted on a Kratos MS-50 (Resolution 10K). EXAMPLE 1 Preparation of tris-(ethoxycarbonylamino)triazine in NN-Dimethyl Acetamide: 10 Potassium cyanate (15 g) was added, under a nitrogen atmosphere, to a mixture of ethanol (9.6 g) and N,N-dimethyl acetamide (60 ml) in a reactor equipped with an efficient condenser and a stirrer. The reaction mixture was heated to 100 C and a solution of cyanuric chloride (3.7 g) in N,N-dimethyl acetamide (20 ml) was then added slowly into the reaction mixture over a period of about 10 minutes. The reaction mixture was kept at 1 00 0 C for 6 hours 15 and thereafter at room temperature overnight. The solvent was then removed in vacuo using a rotary evaporator while maintaining the bath temperature at below 80 0 C. The resulting residue was then added to water (100 ml), the pH adjusted to 7 with concentrated nitric acid, and then extracted with methylene chloride (3 x 50 ml). The organic layers were combined and dried with anhydrous magnesium sulfate, the solvent was evaporated. Addition of 20 acetonitrile gave crude tris-(ethoxycarbonylamino)triazine as a solid (1.5 g, 22% yield). Recrystallization from ethanol gave pure tris-(ethoxycarbonylamino)triazine as white crystals, m.p. 213-2140C (uncorrected). It was identified from its infrared spectrum, nuclear magnetic resonance spectra, exact mass in its electron ionization mass spectrum, and by comparison with an authentic sample prepared by known procedures. IR (KBr): 3257, 2983, 1755, 1608, 25 1492, 1198, 1028, 821 cm- 1 ; 1 H-NMR (300 MHz, DMSO-d 6 ): 6 10.4 (s, NH), 4.2 (q, J=7 Hz,
CH
2 ), 1.2 (t, J=7 Hz, CH 3 ); 13 C-NMR (75 MHz, DMSO-d 6 ): 6 163.7, 150.1, 59.6, 13.1; MSEI (M*): m/z found 342.1321; calculated for C 2
H
1
,N
6 0 6 342.1284. 30 EXAMPLE 2 Preparation of tris-(ethoxycarbonylamino)triazine in NN-Dimethyl Formamide: The procedure of Example 1 was repeated using N,N-dimethyl formamide as the solvent. Sodium cyanate (5.6 g) was added to a reactor containing ethanol (4.7 g) and N,N dimethyl formamide (60 ml). A solution of cyanuric chloride (3.7 grams) in N,N-dimethyl 35 formamide (8 ml) was added (10 minutes). After 6 hours at 1000C and overnight at room temperature, the solution was diluted with methylene chloride (100 ml) and washed twice with 11 WO 99/65883 PCT/US99/10182 water. The organic layer was dried with anhydrous magnesium sulfate. Removal of solvent followed by crystallization using acetonitrile gave tris-(ethoxycarbonylamino)triazine as a white solid (0.4 g, 6% yield). It was identified by «C-NMR to be the desired product. 5 EXAMPLE 3 Preparation of tris-(ethoxycarbonylaminoltriazine in Hexamethyl Phosphoramide: The procedure of Example 1 was repeated using hexamethyl phosphoramide as the solvent. Potassium cyanate (7.5 g) was added to a reactor containing ethanol (4.7 g) and hexamethyl phosphoramide (40 ml). A solution of cyanuric chloride (3.7 grams) in hexamethyl 10 phosphoramide (10 ml) was added (10 minutes). After 6 hours at 1000C and overnight at room temperature, the solution was diluted with methylene chloride (100 ml) and washed twice with water. The organic layer was dried with anhydrous magnesium sulfate. Removal of the solvent gave tris-(ethoxycarbonylamino)triazine as a solution in hexamethyl phosphoramide. It was identified by ‘ 3 C-NMR to be the desired product. 15 EXAMPLE 4 Preparation of tris-(ethoxycarbonylamino)triazine in Sulfolane: The procedure of Example 1 was repeated using sulfolane as the solvent. Potassium cyanate (7.5 g) was added to a reactor containing ethanol (4.7 g) and sulfolane (40 ml). A 20 solution of cyanuric chloride (3.7 grams) in sulfolane (10 ml) was added (10 minutes). After 6 hours at 100 C and overnight at room temperature, the solution was diluted with methylene chloride (100 ml) and washed twice with water. The organic layer was dried with anhydrous magnesium sulfate. Removal of the solvent gave tris-(ethoxycarbonylamino)triazine as a solution in sulfolane. It was identified by 13 C-NMR to be the desired product. 25 Although the present invention is described with reference to certain preferred embodiments, it is apparent that modifications and variations thereof may be made by those skilled in the art without departing from the scope of this invention as defined by the appended claims. 30 12

Claims (18)

1. A process for preparing a 1,3,5-triazine carbamate derivative having the formula (I) or an oligomer thereof: 5 R N QN R 1 00CNH N NHCOOR 2 10 wherein R is selected from the group consisting of -NHCOOR 3 , hydrogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio, amido, sulfonamido, amino, and a leaving group; and 15 wherein R1 , R2 or R 3 is, independently, a hydrocarbyl or a hydrocarbyloxyhydrocarbyl, said process comprising the step of contacting: (i) a 1,3,5-triazine derivative having at least two cyanate-displaceable leaving groups, represented by the formula (II) or an oligomer thereof: 20 L2 L1 N L 25 wherein L’ is selected from the group consisting of hydrogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio, amido, sulfonamido, amino and a leaving group; and wherein each of L 2 and L 3 is, independently, a leaving group; (ii) a cyanate-group containing reagent capable of reaction therewith; 30 (iii) an isocyanate-reactive compound; and (iv) an isocyanate-unreactive organic solvent, wherein said contacting is carried out at a temperature and length of time sufficient to produce a 1,3,5-triazine carbamate derivative having at least two carbamate groups, with the proviso that if the organic solvent is not sufficiently polar to produce a bis-carbamate derivative, 35 contacting is carried out in the presence of a phase-transfer catalyst. 13 WO 99/65883 PCT/US99/10182

2. The process of claim 1, wherein the isocyanate-unreactive organic solvent is a polar solvent having a dipole moment of at least 3.0 Deby Units.

3. The process of claim 1, wherein the isocyanate-unreactive organic solvent has 5 a dipole moment of less than 3.0 Deby Units and contacting is carried out in the presence of a phase transfer catalyst.

4. The process of claim 1, wherein R is -NHCOOR 3 and i, F and R are hydrocarbyl compounds. 10

5. The process of claim 4, wherein the hydrocarbyl compound is an alkyl group having from 1 to 8 carbon atoms.

6. The process of claim 5, wherein R 1 , R 2 and R 3 is, independently, methyl or 15 normal butyl.

7. The process of claim 1, wherein each of Ll , L 2 and L 3 is, independently, a halogen. 20

8. The process of claim 7, wherein the halogen is a chloride.

9. The process of claim 1 wherein cyanate-group containing reagent (ii) is represented by the formula: 25 W(NCO)n wherein n is at least 1; and wherein W is an n-functional moiety selected from the group consisting of metal, hydrogen, quaternary ammonium, quaternary phosphonium, sulfonium, silyl 30 and mixtures thereof.

10. The process of claim 9, wherein W is selected from the group consisting of sodium, potassium, tetraalkylammonium, arlyltrialkylammonium, and a mixture thereof. 35

11. The process of claim 1, wherein the isocyanate-reactive compound (iii) is a hydroxy-functional compound. 14 WO 99/65883 PCT/US99/10182

12. The process of claim 11, wherein the hydroxy-functional compound is an alcohol having from 1 to 20 carbon atoms.

13. The process of claim 12, wherein the alcohol is selected from the group 5 consisting of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, 2-ethyl hexanol, alkyl alcohol, glycidol, stearyl alcohol, 1 methoxy-2-ethanol, 1-ethoxy-2-ethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, isomers thereof, and mixtures thereof. 10

14. The process of claim 13, wherein the alcohol is selected from the group consisting of methanol, butanol and mixtures thereof.

15. The process of claim 1, wherein the isocyanate-unreactive organic solvent is selected from the group consisting of an amide, a phosphorus-containing compound, a 15 sulfone, a sulfoxide, a nitrile, a carbonate, a lactone, a nitro compound, a diketone, a keto alcohol, a ketone, an ether, an ester, a hydrocarbon, a halocarbon, and a mixture thereof.

16. The process of claim 15 wherein the isocyanate-unreactive solvent is selected from the group consisting of N,N-dimethyl acetamide, N-methyl pyrrolidone, N,N-dimethyl 20 formamide, hexamethyl phosphoramide (HMPA), hexamethyl phosphorus triamide (HMPT), dimethyl sulfone, sulfolane, acetonitrile, propionitrile, benzonitrile, ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, butyrolactone, propiolactone, nitromethane, nitroethane, nitropropane, nitrobenzene, acetyl acetone, diacetone alcohol, methyl acetate, ethyl acetate, ethyl formate, methoxypropyl acetate, acetone, methyl ethyl 25 ketone, methyl iso-propyl ketone, methyl iso-butyl ketone, cyclohexanone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, benzene, toluene, ethyl benzene, xylene, mesitylene, hexane, heptane, cyclohexane, methylene chloride, chlorobenzene, 1,1,1 -trichloroethane, anda mixtures thereof. 30

17. The process of claim 16 wherein the isocyanate-unreactive organic solvent is a polar solvent selected from the group consisting of N,N-dimethyl acetamide, N-methyl pyrrolidone, N,N-dimethyl formamide, hexamethyl phosphoramide (HMPA), hexamethyl phosphorus triamide (HMPT), dimethyl sulfone, sulfolane, dimethyl sulfoxide, acetonitrile, propionitrile, benzonitrile, ethylene carbonate, propylene carbonate, butylene carbonate, 35 dimethyl carbonate, butyrolactone, propiolactone, nitromethane, nitroethane, nitropropane, nitrobenzene, acetyl acetone, diacetone alcohol, and mixtures thereof. 15 WO 99/65883 PCT/US99/10182

18. The process of claim 16, wherein the isocyanate-unreactive solvent is a non polar solvent selected from the group consisting of methyl acetate, ethyl acetate, ethyl formate, methoxypropyl acetate, acetone, methyl ethyl ketone, methyl iso-propyl ketone, methyl iso-butyl ketone, cyclohexanone, ethylene glycol dimethyl ether, diethylene glycol 5 dimethyl ether, triethylene glycol dimethyl ether, benzene, toluene, ethyl benzene, xylene, mesitylene, hexane, heptane, cyclohexane, methylene chloride, chlorobenzene, 1,1,1 trichloroethane, and mixtures thereof. 16

AU39789/99A
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Process for the preparation of a reaction mixture containing alkoxycarbonylaminotriazine

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triazine derivatives

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Simulation Method, Simulation Apparatus, Biological Treatment Method, and Biological Treatment Apparatus

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American Cyanamid Company
Triazine crosslinking agents and curable compositions containing the same

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American Cyanamid Company
Triazine crosslinking agents and curable compositions

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A process for preparing a triazine tris-lactam crosslinking agent and curable compositions containing the same

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Aminoresin based coatings containing 1,3,5-triazine tris-carbamate co-crosslinkers

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1993-05-14
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