Patent GB-852540-A (GB)
Title: Alkylidene bis indanols
IPC: C07C39/17
Filed: 1957-08-28
Abstract: The deterioration of rubber is retarded by the incorporation therein of an alkylidene bis indanol of the general formula: <FORM:0852540/IV(a)/1> wherein the -OH groups are either in the two 4-or the two 5- positions, an alkyldene bridging group is attached at either the 5-positions or the 7-positions when the OH groups are in the 4-positions or at the 4- or the 6-positions when the OH groups are in the 5- positions, R, R1 and R11 are hydrogen atoms or hydrocarbon radicals having 1 to 8 carbon atoms, and n is either 1 or 2.  The compounds are made by reacting 4- or 5-indanol or a substituted indanol with an aldehyde (see Group IV(b)).  The compounds impart to the vulcanized rubber remarkably high anti-flex-cracking properties and excellent heat-stabilizing properties, as well as effective resistance to the loss of tensile strength.  Furthermore, the compounds are non-staining, and hence are well-adapted for use in white rubber stocks.  In examples, four tread stock recipes are compounded having the following ingredients :-natural crude rubber (100 parts by weight), carbon black (50 parts), zinc oxide (5 parts), stearic acid (3 parts), sulphur (3 parts), bis(2-benzothiazyl)-disulphide (1 part), and an alkylidene bis-indanol (1 part); the latter being a bis (methylidene) bis (5- indanol), or a (bis) methylidene bis (4-indanol), or 4, 41-methylidene bis (6 - t - butylated - 5 - indanol), or 6, 61 - benzylidene bis (5 - indanol).  Comparison stocks are also compounded which contain phenyl-beta-napthylamine in place of the alkylidene bis-indanol, and which contain no deterioration retarded at all. The compounded stocks are cured and aged, and then subjected to tensile-strength and flexing tests, the results of which show that the products containing an alkylidene bis-indanol have superior properties compared to the others.ALSO:The invention comprises alkylidene bisindanols of the general formula: <FORM:0852540/IV(b)/1> wherein the -OH groups are either in the two -4 or the two 5-positions, an alkylidene bridging group is attached at either the 5-positions or the 7-positions when the OH groups are in the 4-positions or at the 4- or the 6-positions when the OH groups are in the 5-positions, R,R1 and R11 are hydrogen atoms or hydrocarbon radicals having 1 to 8 carbon atoms, and n is either 1 or 2.  The compounds are made by reacting 4- or 5-indanol or a substituted indanol with an aldehyde in the presence of a catalyst such as sulphuric acid, p-toluene sulphonic acid, or hydrochloric acid.  The compounds may be used as deterioration-inhibitors for rubber products (see Group V).  In example 1, a mixture of 5-indanol, formalin, benzene and a small proportion of concentrated hydrochloric acid is slowly warmed, over a period of about 4 hours, to about 65 DEG C., and maintained at this temperature for 2 1/2 hours.  The reaction product is poured into water, and allowed to separate into an organic layer and a water layer. The organic layer is washed with aqueous sodium bicarbonate and then with water; and the benzene is evaporated off.  The residue comprises a bis(methylidene) bis(5-indanol).  In Example 4, benzaldehyde is reacted with 5-indanol to produce 6,61-benzylidene bis(5-indanol).  In example 8, para-aldehyde is reacted with 6-t-butylated-5-indanol to produce 4,41-ethylidene bis(6-t-butylated-5-indanol).  In example 10, formaldehyde is reacted with 1,1-dimethyl-3-isopropyl-5-t-butylated-4-indanol to produce 7,71-methylidene bis(1,1-dimethyl-3-isopropyl-5-t-butylated-4-indanol).