Patent GB-894620-A (GB)
Title: Improvements in and relating to the preparation and use of polynuclear polyphenols and the resulting polyphenols and materials for example polymer compositions containing such polyphenols
IPC: C10L1/183
Filed: 1960-09-26
Abstract: A composition comprises a normally oxidizable organic material such as gasoline, fuel and lubricating oils, greases and edible oils such as vegetable oils and lard and as antioxidant, a 1, 4-bis-(3, 5-di-alkyl-hydroxy benzyl)-tetra-alkyl benzene in which each alkyl radical contains up to 8 carbon atoms.  An example describes the addition of 1, 4-bis-(3, 5-di-tert. butyl-4-hydroxy benzyl) durene to a commercial gasoline.  Specifications 799,392, 799,823, 803,198 and 830,824 are referred to.ALSO:A composition comprises a solid polymer of an alpha-olefin and a small amount not exceeding 5% by weight of the polymer of a polynuclear polyhydric phenol of the formula <FORM:0894620/IV (a)/1> where R is an alkyl radical of 1 to 8 carbon atoms, each R1 is a hydrocarbon radical of 1 to 8 carbon atoms or hydrogen or halogen atom, n is 0 or 1, m is 0, 1, 2 or 3, p is 1, 2 or 3, the sum of m and p being from 18 to 5 and in which formula both terminal aromatic rings can be mono- or poly-nuclear.  Examples describe the incorporation of various polyhydric phenols, including the preferred 1, 4-bis-(3, 5-dialkyl-hydroxybenzyl) tetra-alkyl benzenes, into polyethylene and polypropylene and compare the properties of these compositions with those containing conventional antioxidants.  1,4-bis-(3, 5-dialkyl-hydroxybenzyl)1 tetra alkyl benzenes may also be used as antioxidants for elastomers such as natural and synthetic rubbers, and an example describes the use of 1, 4-bis-(2-hydroxy-3-tert.- butyl-5-methyl-benzyl)-and-(2-hydroxy-3, 5-dimethylbenzyl) durene in pale crepe rubber compositions. Specifications 799,392, 799,823, 803,198 and 830,824 are referred to.ALSO:The invention comprises 1,4-bis-(3,5-dialkylmono- or di-hydroxybenzyl) tetra-alkylbenzenes where each alkyl radical has up to 8 carbon atoms and a process for their preparation by reacting in the liquid phase and at a temperature in excess of about 50 DEG C. (a) a dialkyl phenol where two of the three ring carbon atoms ortho and para to the hydroxyl group are substituted with alkyl radicals having up to 8 carbon atoms and the third ring carbon atom has a replacable hydrogen atom with (b) a tetraalkyl benzene where each of the alkyl radicals has up to 8 carbon atoms and the 1 and 4 ring carbon atoms are each substituted with a halomethyl, hydroxymethyl or acetoxymethyl radical.  1, 4 - bis - (3, 5 - di - tert.alkyl - 4 - hydroxy - benzyl)-tetra-alkylbenzenes are preferably prepared by an alternate process which comprises reacting in an inert organic solvent having a dielectric constant of at least about 20 an alkali metal salt of a 2,6-di-tert.alkylphenol with a 1,4-bis-(halomethyl)tetra-alkylbenzene.  Examples describe the preparation of 1,4-bis-(2-hydroxy-3-tert.butyl - 5 - methyl-, 2 - hydroxy - 3, 5 - di - methyl -, 2 - hydroxy - 3 - tert.butyl - 5 - ethyl - 2-hydroxy-3-octyl-5-ethyl and 4-hydroxy-3,5-di-tert. butyl - benzyl) durene and 1, 4- bis - (2, 4 - dihydroxy - 3 - tert.butyl - 5 - methylbenzyl) - durene.  The Specification refers also to polyhydric phenols of the formula <FORM:0894620/IV (b)/1> where R is an alkyl radical of 1-8 carbon atoms, each R1 is a hydrocarbon radical of 1-8 carbon atoms, a halogen atom or a hydrogen atom, n is 0 or 1, m is 0, 1, 2 or 3, p is 1, 2 or 3, the sum of m and p being from 1 to 5, and in which formula both terminal aromatic rings can be mononuclear or polynuclear.  These phenols may be prepared by methods analogous to those described above using bis-halo- or halomethyl hydroxy or hydroxymethyl or acetoxymethyl tetra-alkyl benzenes and the appropriate phenol. Lists of suitable reactants are given. Examples describe the preparation of (4-hydroxy-benzyl) and (2 - hydroxy - 5 - chlorobenzyl) - durene, 1, 4 - bis - (2 - hydroxy - 5 - octyl - benzyl) - tetrabutyl benzene, and 1, 2 - bis - (2, 3 - di - hydroxybenzyl) durene.  1, 4 - bis - (2 - hydroxy - 3 - tert.butyl - 5 - methylphenyl) durene and 1, 3 - bis (2, 4 - dihydroxy - 3, 6 - di - tert.butyl - 5-methyl-benzyl) tetramethyl benzene are also mentioned.  1, 4-bis-(chloromethyl)-durene may be prepared by reacting durene with formaldehyde and hydrogen chloride. 1,4-bis-(hydroxymethyl)-tetra-alkyl benzenes may be prepared by hydrolysing the bis halomethyl compounds and 1,4-bis - (acetoxymethyl) - tetra - alkyl benzenes may be prepared by reacting the bis-halomethyl compound with silver or sodium acetate.  Alkali metal derivatives of 2,6-di-tert.alkyl phenols, which may be represented by the tautomeric formulae <FORM:0894620/IV (b)/2> may be prepared by treating the phenol with an alkali metal alcoholate, e.g. potassium tert.-butoxide, in a polar solvent, e.g. dimethyl formamide.  Sodium and potassium salts of 2,6-di-tert.butyl phenol are prepared.  Specifications 799,392, 799,823, 803,198 and 830,824 are referred to.