Patent GB-984376-A (GB)
Title: Production of amino-s-triazines
Inventor: CARNELL PETER JOHN HERBERT
IPC: C08G73/06
Filed: 1962-09-07
Abstract: Amino-s-triazines are prepared by reacting ammonia or a primary or secondary amine with an s-triazine carrying linked to carbon one or more -OR1 and/or -SR1 groups, wherein R1 is a substituted or unsubstituted hydrocarbon group, in the presence of at least one of the following substances:-  substituted or unsubstituted alkali metal phenoxides; alkali metal alkoxides; anhydrous salts of transition metals in their lower oxidation states; cupric salts and complexes; straight-chain carboxylic acids boiling above 200 DEG  C. and their salts; oxides of transition metals and rare earth metals; alkali metal and ammonium salts of transition metal oxy-acids; halides having activity as Friedel-Crafts catalysts; lead and tin compounds; magnesium compounds; and sulphonic acids.  The ring carbon atoms of the s-triazine reactants that are not linked to OR1 or SR1 groups may be linked to hydrogen atoms or R, NR1R2, OH, NHCOR or NHSO2R groups, wherein R, R1 and R2 are unsubstituted or substituted hydrocarbon groups, or to primary or secondary amino groups and the amine reactant may have the amino groups attached to substituted or unsubstituted hydrocarbon or heterocyclic radicals. The catalyst is usually employed in an amount from 0.01 to 1% by weight of the s-triazine reactant and may be used in conjunction with one or more zinc compounds.  It is preferable to perform the reaction in the liquid phase and, for polymer formation, to remove the alcohol, thiol, phenol or thiophenol produced as the reaction proceeds by, for example, passing a stream of inert gas through the reaction vessel. The products are monomers when monofunctional reactants are used or polyfunctional reactants are reacted at below about 100 DEG  C. and are polymers when polyfunctional reactants are reacted at higher temperatures, e.g. 200 DEG  to 300 DEG  C. (see Division C3).  In one embodiment of the invention the process may be performed by reacting one or more s-triazines containing both OR1 and/or SR1 groups and primary and/or secondary amino groups.  Specifications 963,811, 963,812, 963,814 and 963,815 are referred to.ALSO:Polymers comprising a succession of repeating units of the formula <FORM:0984376/C3/1> wherein A is a hydrogen atom or a substituted or unsubstituted hydrocarbon or heterocyclic group, the A's being the same or different, D is a substituted or unsubstituted hydrocarbon or heterocyclic group, X is H, -R, -NH2, -NHR, -NR1R2, OH, -OR1, -SR1, -NHCOR or NHSO2R where R, R1, R1 and R2 are substituted or unsubstituted hydrocarbon groups and m is at least 1, are produced by reacting one or more amines of the formula AHN-D(-NHA)m with one or more s-triazines carrying linked to carbon two or more -OR1 and/or SR1 groups in the presence of at least one of the following substances: substituted or unsubstituted alkali metal phenoxides; alkali metal alkoxides; anhydrous salts of transition metals in their lower oxidation states; cupric salts and complexes; straightchain carboxylic acids boiling above 200 DEG  C. and their salts; oxides of transition metals and rare earth metals alkali metal and ammonium salts of transition metal oxy-acids; halides having activity as Friedel-Crafts catalysts; lead and tin compounds; magnesium compounds; and sulphonic acids.  The ring carbon atoms of the s-triazine reactants that are not linked to -OR1 or SR1 groups may be linked to hydrogen atoms or -R1, -NR1R2, -OH, NHCOR, or NHSO2R groups or to primary or secondary amino groups.  The catalyst is usually employed in an amount from 0.01 to 1% by weight of the s-triazine reactant and may be used in conjunction with one or more zinc compounds. It is preferable to perform the reaction in the liquid phase and to remove the alcohol, thiol, phenol or thiophenol produced as the reaction proceeds by, for example, passing a stream of inert gas through the reaction vessel.  A reaction temperature of 200 DEG to 300 DEG C. is usually employed since monomers (see Division C2) tend to be formed at lower temperatures, usually below 100 DEG C. The polymers of the above formula may also be prepared by reacting said monomers of formula <FORM:0984376/C3/2> with themselves or one or more other monomers of said formula in the presence of at least one of the above specified catalysts. In one embodiment of the invention polymers comprising a succession of repeating units of formula <FORM:0984376/C3/3> are prepared by A) reacting a compound of formula <FORM:0984376/C3/4> with itself or one or more compounds of the same formula or (B) reacting at least one compound of formula <FORM:0984376/C3/5> with at least one compound of formula <FORM:0984376/C3/6> The examples relate to the polymerization of 2 - phenoxy - 4 - (4 - para - aminophenyl-sulphonylphenylamino) - 6 - phenyl - s - triazine in the presence of various catalysts. Specifications 963,811, 963,812, 963,814 and 963,815 are referred to.