Patent GB-1116127-A (GB)
Title: Process for the production of antioxidants which contain sulphur
IPC: C09K15/14
Filed: 1967-02-01
Abstract: Polyolefins are stabilized by incorporating into them 0.05-5% by weight of an anti-oxidant of Formula III <FORM:1116127/C3/1> wherein one of X1 and X2 and one of X11 and X12 is a hydroxyl group and the other is hydrogen; R1 and R11 are C3- 20 alkyl which is branched at the a  carbon atom and may be substituted by phenyl or C5- 20 cycloalkyl having a 5-12 membered ring; R2 and R12 are hydrogen, C1- 8 straight chain alkyl, optionally substituted phenyl or the same as R1; R3, R13, R4 and R5 are hydrogen or C1- 6 alkyl; R6 is hydrogen, C1- 19 alkyl, C2- 19 oxa-alkyl o thiaalkyl; R7 is hydrogen or methyl; R8 is hydrogen or methyl and when R7 is hydrogen R8 may also be C2- 6 alkyl.  In examples, polypropylene is stabilized by 1,1-bis-(3-tert.-butyl-4-hydroxy - 6 - methylphenyl) - 3 - dodecylthiobutane and polyethylene is stabilized by 1,1 - bis - (2 - methyl - 4 - hydroxy - 5 - tert.-butyl - phenyl) - 3 - dodecylthiobutane or by 1,1 - bis - (2 - methyl - 4 - hydroxy - 5 - tert.-butylphenyl) -3-dodecylthio propane.ALSO:Novel compounds of Formula III wherein one of X1 and X2 and one of X11 and X21 represents a hydroxyl group and the other represents hydrogen, R1 and R11 each represent C3- 20 alkyl which is branched at the a -carbon atom and which may contain a phenyl radical which may be substituted, or C5- 20 cycloalkyl having a 5 to 12 membered ring; R2 and R21 each represent hydrogen, a C1- 8 straight chain alkyl, optionally substituted phenyl or the same as R1; R3 and R31, R4 and R5 each represent hydrogen or C1- 6 alkyl; R6 represents hydrogen C1- 9 alkyl, C2- 19 oxa-alkyl or thia-alkyl; R7 represents hydrogen or methyl and R8 hydrogen or methyl and when R7 is hydrogen R8 may be C2- 6 alkyl; are prepared by reacting two mols. of identical or different hydroxyaryl compounds of Formula I with one mol. of an aldehyde of Formula II; or by condensing 1 mol. of a diphenyl methane compound of Formula IV in which Y can be split off as non-basic HY, with 1 mol. of a mercaptan HS-CR6R7R8; or by reacting 1 mol. of a diphenyl methane compound of Formula VII with at least two mols. of olefins of formula R10CH = CR9R11 wherein R9 is hydrogen or methyl, R10 is hydrogen or C1- 8 alkyl, R11 is C1- 18 alkyl or optionally substituted phenyl or R10 and R11 together represent a polymethylene group, optionally substituted by C1- 5 alkyl groups and having, in all, 3-10 methylene groups and 3-18 carbon atoms, in the presence of acid catalysts. Typical examples of compounds of Formula III are 1,1 - bis - (2 - methyl - 4 - hydroxy - 5 tert. butylphenyl) - 3 - dodecylthiobutane and the 5-cyclohexylphenyl analogue; 1-(2-methyl-4-hydroxy - 5 - tert. butylphenyl) - 1 - (2-methyl - 4 - hydroxy - 5 - tert. amylphenyl) - 3-dodecylthiobutane; 1,1 - bis - (2 - methyl - 4-hydroxy - 5 - tert. butylphenyl) - 3 - (2 - dodecylthioethyl) thiobutane and the 3 - (2-octyloxyethyl) analogue; 1,1 - bis - (4 - hydroxy - 3,5 - di - tert. butyl phenyl) - 3 - dodecylthiobutane; and of intermediates prepared are 3 - butylthiopropionaldehyde; 1,1 - bis-(2 - methyl - 4 - hydroxy - 5 - tert. butylphenyl) - 3 - chlorobutane, and the 3 - bromobutane analogue and 1,1 - bis - (4 - hydroxy phenyl) - 3 - dodecylthio butane.  The compounds III are used as antioxidants for organic materials, and in particular for polyolefins. <FORM:1116127/C2/1> <FORM:1116127/C2/2> <FORM:1116127/C2/3> <FORM:1116127/C2/4> <FORM:1116127/C2/5>