Patent GB-1005241-A (GB)
Title: Thio-derivatives of polyacid anhydrides and resinous compositions derived therefrom
IPC: C07D307/89
Filed: 1963-06-04
Abstract: Resinous products are obtained by reacting at least one polyepoxide or at least one polyhydroxy compound with a thioxy-polyacid anhydride of the formula <FORM:1005241/C3/1> wherein n is at least 2, R is an n-valent organic radical such that at least 2 of the S atoms are no more than 6 carbon atoms removed from each other or from a -COO-, -OH-, -O- or -CO- group, R1 is a hydrocarbon chain of 0-3 carbon atoms which may be substituted by alkyl groups, S being directly connected to the anhydride ring when the number of carbon atoms is 0, R2 may be (1) not connected to R1 when R2 is a hydrogen or chlorine atom, (2) singly connected to R1, when R2 is -CH2-CH2- or (3) doubly connected to R1 when R2 is <FORM:1005241/C3/2> which may be alkyl substituted, and R3 and R4 are hydrogen atoms or alkyl groups. Polyepoxides which may be cured with these compounds include glycidyl ethers and esters, e.g. those based on Bisphenol A, Novolaks, glycerol, 1,4-butanediol and poly-glycidyl acrylate, and epoxides of the vinyl and epoxy cyclohexane type.  Examples 21-23 describe the preparation of epoxy resins.  Any polyhydroxyl compound can be used for making the polyesters, e.g. starches, polyvinyl alcohols, polyallyl alcohols, glycols, glycerol, hydrogenated sugars, trimethylol ethane, trimethylol propane, pentaerythritols and, preferably, the partial esters of polyhydric alcohols.  Examples 24-26 describe the preparation of polyester resins using as the polyhydric alcohol (24) the reaction product of dimerized soya bean acid and trimethylol propane (25 hydrogenated bisphenol A (26) trimethylol propane.  The thioxypoly acid anhydrides are prepared from polymercaptans R(SH)n, preferably polymercapto acid esters. Example 8 describes the preparation of the mercaptoacetate of a copolymer of allyl alcohol and styrene.ALSO:The invention comprises thioxy-polyacid anhydrides of the general formula <FORM:1005241/C2/1> wherein n is at least 2, R is an n-valent organic radical such that at least two of the S atoms are no more than 6 carbon atoms removed from each other or from a -COO-, -OH,-O-or -CO- group, R1 is a carbon chain of 0-3 atoms, S being directly connected to the acid anhydride ring when the number of carbons is 0, where the number of carbons is greater than 0 R1 being a hydrocarbon or alkyl-substituted hydrocarbon radical and wherein R2 may be (1) not connected to R1, (2) singly connected to R1 or (3) doubly connected to R3 and when (1) R2 is a hydrogen or chlorine atom, (2) R2 is -CH2-CH2- and (3) R2 is <FORM:1005241/C2/2> which may be substituted by alkyl groups and R3 and R4 are hydrogen atoms or alkyl groups. The compounds are made by heating an acid anhydrid in which the anhydride group is part of a 5-membered ring and which contains a double bond, either in the ring, between the ring and the exocyclic carbon atoms or between two exocyclic carbon atoms so that the double bond is a ,b ; b ,g  or g ,d  relative to the carbonyl of the anhydride, with a polymercaptan of the formula R(SH)n.  The preferred polymercaptans are the polymercapto acid esters, especially polymercapto-acetates and -propionates, prepared from polyhydroxy compounds, e.g. pentaerythritols, trihydric alcohols, partial esters of polyhydric alcohols, glycols, starches and castor oil. Other suitable polymercaptans include 1,4-butane-dithiol, 2,3-dimercaptopropanol, toluene - 3,4 - dithiol, a ,a 1 - dimercapto - p - xylene and mercapto alcohol esters of polycarboxylic acids.  The preferred unsaturated anhydride starting materials are maleic anhydride and its alkyl or chlorine substituted derivatives, e.g. methyl maleic and chloromaleic anhydrides. Also suitable are the anhydrides containing terminal olefin groups, e.g. itaconic anhydride and allyl succinic anhydride and those containing a 6-membered ring fused to the anhydride ring, e.g. tetrahydrophthalic anhydride and methyl - bicyclo - [2,2,1] - hept - 5 - ene - 2,3 - dicarboxylic anhydride. The compounds of the invention are used as cross-linking agents for polyepoxides and for preparing polyesters with polyhydroxy compounds (see Division C3). Examples 1-12 describe the preparation of polymercapto acid esters used as starting materials. Examples 13-20 relate to the preparation of the novel compounds.