Patent GB-779025-A (GB)
Title: Dibasic carbocyclic acids and derivatives thereof
IPC: C08G69/42
Filed: 1955-02-15
Abstract: The compounds prepared by reacting one mole. of a compound of formula HS.CH2.X.CH2.SH wherein X is a phenylene, or divalent naphthalene or cyclohexane radical which may be alkylated, with at least two moles. of an acrylic compound of formula CH2=CR.Y, wherein R is a hydrogen or chlorine atom or a methyl or ethyl radical and Y is a carboalkoxy or cyano radical (see Group IV (b)) are used in the formation of resins and fibre-forming polymers.  The compounds obtained are dicyano or dicarboalkoxy compounds, the dicyano compounds being converted into the corresponding acids or esters by known methods, The acids, or preferably the esters, may be condensed with various difunctional compounds such as glycols, e.g. hexamethylene glycol, diamines, e.g. hexamethylene diamine, dimercaptans, alkylolamines, hydroxymercaptans or aminomercaptans.  When the carboxy groups are in paraposition fibre-forming resins are obtained.  In an example, bis - b  - carboxyethylthiomethyldurene and hexamethylene diamine are polycondensed by heating together in the presence of nitrogen and then under vacuum to give a fibre forming product of formula (-OC.(CH2)2.SCH2.X.CH2S. (CH2)2.CO.NH (CH2)6.NH-)n wherein X is a 2:3:5:6-tetramethyl phenylene radical.ALSO:The invention comprises the compounds bis-b -carboxyethyl-thiomethyl durene, bis-b -carbomethoxyethyl - thiomethyl - durene and bis-b -cyanoethyl-thiomethyl-durene, and a process for preparing them and other similar compounds, wherein one mole. of a compound of formula HS.CH2.X.CH2.SH, wherein X is a phenylene or divalent naphthalene or cyclohexane radical which may be alkylated, is reacted with at least two moles. of an acrylic compound of formula CH2=CR.Y, wherein R is a hydrogen or chlorine atom or a methyl or ethyl radical and Y is a carboalkoxy or cyano radical.  Specified bis-mercaptomethyl compounds are bis-mercaptomethyl-durene (i.e. 1 : 2 : 4 : 5 - tetramethyl - 3 : 6 - dimercaptomethyl-benzene), parabismercaptomethyl-benzene, 2 : 5 - bismercaptomethyl - toluene, 1 : 4-bismercaptomethyl-2 : 5-dimethylbenzene, 1 : 4-or 2 : 6- or 2 : 7-bismercaptomethyl-naphthalene ortho - bismercaptomethyl - toluene, bis-mercaptomethyl-isodurene 1 : 2 : 4 : 5-tetramethyl-3 : 6 - dimercaptomethyl - cyclohexane and 1-methyl - 2 : 5 - bismercaptomethyl - cyclohexane.  Specified acrylic compounds are acrylonitrile methacrylonitrile, ethacrylonitrile, chlorocrylonitrile, methylacrylate, methyl methacrylate. isopropyl acrylate and ethyl chloracrylate.  The cyano compounds may be converted into the corresponding carboalkoxy compounds by alcoholysis, and the carboxy compounds may be obtained by hydrolysis of the carboalkoxy compounds.  The reagents are mixed in a ratio of at least about 2 moles. of acrylic compound per mole. of dimercaptan, but an excess of up to 10 moles. of acrylic compound is preferred and acts as a solvent. Other solvents such as benzene, toluene, xylene, methyl ethyl ketone and dimethyl formamide may be used but tend to retard the reaction.  Acid or basic catalysts such as sodium methoxide, trimethylbenzylammonium hydroxide, tetramethylammonium hydroxide, hydrogen chloride or toluene sulphonic acid in amounts from about 0.5 to 10 per cent may be used, the quaternary ammonium bases being preferred.  About 0.1 to 2 per cent of a polymerization inhibitor such as hydroquinone, phenyl-b -naphthylamine or 2 : 6-di-tert.-butyl-4-methyl-phenol may also be used.  The di-acids and di-esters of the invention may be reacted with various difunctional compounds to give resins and fibre-forming polymers (see Group IV (a)).  In examples: (1) bis-mercaptomethyl-durene is reacted with methyl acrylate in the presence of hydroquinone and trimethylbenzylammonium hydroxide to give bis - b  - carbomethoxyethyl - thiomethyl-durene which is hydrolysed with alcoholic potassium hydroxide to give bis-b -carboxyethyl-thiomethyl-durene; (2) as in (1) but using acrylonitrile, bis b -cyanoethyl-thiomethyl durene is obtained and reacted with methanol in the presence of hydrogen chloride to give the corresponding carbomethoxy compound.