Patent GB-964985-A (GB)
Title: Sulphur-containing s-triazines
Inventor: RIDGWELL STANLEY ARTHUR
IPC: C08G75/00
Filed: 1961-04-18
Abstract: The invention comprises s-triazines of the structure <FORM:0964985/C1/1> where n is 0 or 1 and Z is D1-S or S where D1 is an alkylene or arylene group, X is hydrogen or a substituted or unsubstituted hydrocarbon group and Y is the same as X or -ST where T is an s-triazine group. X may be aliphatic, especially C 1-6 alkyl, e.g. methyl, or an aromatic group, e.g. phenyl, and may be substituted, e.g. a halogenated hydrocarbon group, such as trifluoromethyl. The invention also provides polymers containing the repeating units <FORM:0964985/C1/2> <FORM:0964985/C1/3> The preferred compounds are those in which n = O and Y is the same as X and are prepared by the reaction of an s-triazine carrying a replaceable group, e.g. halogen atom and an s-triazine containing a mercapto group, preferably in the presence of an acid binding agent, e.g. aqueous alkali or tertiary amine. s-Triazines in which n = O and one or more of the groups Y is -ST are prepared either by the reaction of an s-triazine carrying two replaceable groups, e.g. halogen atoms, with an s-triazine containing one thiol group, or by the reaction of an s-triazine having two thiol groups and s-triazine carrying one replaceable group, e.g. halogen atom. s-Triazines in which n = 1 and Z is S are prepared by treating the 2-mercapto substituted triazines with a mild oxidising agent, e.g. bromine water. Those compounds in which n = 1 and Z is D1-S are obtained by condensing a difunctional hydrocarbon derivative having two readily eliminated groups, e.g. a dihalogeno alkene, with two equivalents of a non-functional mercapto-s-triazine or a dimercapto-hydrocarbon and two equivalents of an s-triazine carrying one replaceable group in the presence of an acid binding agent; the reaction is conveniently carried out in a 2-phase emulsified system. Polymeric compounds of the formula I or II are obtained by the reaction of an s-triazine carrying two replaceable groups and a dimercapto s-triazine or dimercapto-hydrocarbon respectively. Those compounds of formula III may also be obtained by condensing a dimercapto-s-triazine with a compound containing two replaceable groups attached to -D1-; this reaction can be effected in a melt at 200 DEG C. and above.  The group D1 may be an alkylene group, e.g. -(CH2)p-where p is 1 to 10 or, preferably, an arylene group such as meta- or para-phenylene. Examples describe the preparation of (1 and 2) 4:6:41:61-tetraphenyl-di-s-triazinyl-2-sulphide, (3) bis-4:6-diphenyl-triazine-2:21-disulphide, (4 and 5) tri- and penta-methylene-bis-(4:6-dipehynl-s-triazine-2-)sulphide, (6) a polymer of 2-phenyl-4:6-dichloro-s-triazine and dithioresorcinol and (7) a polymer of 2:4-dimercapto-6-phenyl-s-triazine and 2:4-dichloro-6-phenyl-s-triazine.ALSO:The invention comprises polymeric sulphur containing s-triazines containing the repeating units <FORM:0964985/C3/1> <FORM:0964985/C3/2> where X is hydrogen or a substituted or unsubstituted hydrocarbon group and D1 is an alkylene or arylene group, X may be an aliphatic group, e.g. 1-6C alkyl such as methyl, or a substituted aliphatic group such as trifluoromethyl or an aromatic group, e.g. phenyl.  Polymers of the type II are prepared by the reaction of an s-triazine containing two replaceable groups, e.g. halogen atoms, with a dimercapto-s-triazine. Compounds of the formula III are prepared by condensing a dimercapto-s-triazine with a molar equivalent of a compound containing two readily eliminated groups attached to the residue -D1-, or, preferably, condensing an s-triazine carrying two replaceable groups with a molar equivalent of a dimercaptan HS-D1-SH; the reaction may be carried out in a melt at 200 DEG C. or above. The linear polymers can be cross-linked by the inclusion of a trifunctional derivative or can be limited in molecular weight by the use of a proportion of a monofunctional reactant. Example 6 describes the preparation of a polymer from dithio resorcinol and 2-phenyl-4:6-dichloro-s-triazine and in Example 7 a low molecular weight polymer is obtained from 2:4-dimercapto-6-phenyl -striazine and 2:4-dichloro -6- phenyl -s-triazine.