Patent GB-771118-A (GB)
Title: Resinous polymerisation products
IPC: C08F16/02
Filed: 1954-04-01
Abstract: Primary alkenyl monohydric phenolic compounds or mixtures thereof of the formula <FORM:0771118/IV(a)/1> wherein R is an aromatic radical having one hydroxyl group directly attached to a ring and R1 is hydrogen or an aliphatic radical or the ether form <FORM:0771118/IV(a)/2> wherein R is an aromatic radical, are polymerized in the presence of a catalyst to give a product of the formula <FORM:0771118/IV(a)/3> where n is 2 to 10.  In examples, 2-allyl-4-methyl phenol, allyl-p-tolyl ether, allyl cresol, and allyl-b -naphthol are polymerized by heating with zinc chloride and hydrogen chloride as catalyst.  The monomers are prepared by reacting phenols, cresols, xylenols, ethyl-, propyl-, chloro-, nitro-, octyl-, t-butyl-, mono- and di-a -phenyl ethyl phenols and naphthols with primary alkenyl, e.g. allyl and methallyl compounds and a list is given. In a preferred process, a b -halogen substituted allyl compound is reacted with the phenol and the hydrogen halide produced together with added metal halide forms the catalyst.  Catalysts mentioned are zinc, tin, aluminium, iron, antimony, nickel and magnesium chlorides, fluorides, bromides, iodides and sulphates in combination with hydrogen halides, concentrated sulphuric and chlorosulphuric acids and boron trifluoride etherates.  The products may be used as antioxidants for natural and synthetic rubbers such as polychloroprene, butadiene-styrene, isobutylene-butadiene or isoprene, and butadiene-acrylonitrile copolymers, and oil or petrol and their use is exemplified in a composition of pale crepe rubber, zinc oxide, calcium carbonate, sulphur, hexamethylene tetramine and stearic acid.ALSO:Primary alkenyl monohydric phenolic compounds or mixtures thereof of the formula <FORM:0771118/IV(b)/1> wherein R is an aromatic radical having one hydroxyl group directly attached to a ring and R1 is hydrogen or an aliphatic radical, or the ether form <FORM:0771118/IV(b)/2> wherein R is an aromatic radical, are polymerized in the presence of a catalyst to give a product of the formula <FORM:0771118/IV(b)/3> where n is 2 to 10.  In examples, 2-allyl-4-methyl phenol, allyl-p-tolyl ether, allyl cresol, and allyl-b -naphthol are polymerized by heating with zinc chloride and hydrogen chloride as catalyst.  The monomers are prepared by reacting phenols, cresols, xylenols, ethyl-, propyl-, chloro-, nitro-, octyl-, t.-butyl, mono- and di-a -phenyl ethyl phenols and naphthols with primary alkenyl, e.g. allyl and methallyl compounds, and a list is given.  In a preferred process a b -halogen substituted allyl compound is reacted with the phenol and the hydrogen halide produced, together with added metal halides forms the catalyst. Catalysts mentioned are zinc, tin, aluminium, iron, antimony, nickel and magnesium chlorides, fluorides, bromides, iodides and sulphates in combination with hydrogen halides, concentrated sulphuric and chlorosulphuric acids and boron trifluoride etherates.  The products may be used as anti-oxidants for natural and synthetic rubber, oil and petrol.ALSO:Polymers of primary alkenyl monohydric phenol compounds or mixtures thereof of the formula <FORM:0771118/III/1> wherein R is an aromatic radical having one hydroxyl group directly attached to a ring, R1 is hydrogen or an aliphatic radical and n is 2 to 10 are used as antioxidants for oils and petrol.  In examples, the polymers are derived from 2-alkyl-4-methy phenol, alkyl-o-tolyl, ether, allyl cresol, and allyl-b -naphthol.ALSO:Polymers of primary alkenyl monohydric phenol compounds or mixtures thereof of the formula:  <FORM:0771118/V/1> wherein R is an aromatic radical form, or the ether form having one hydroxyl group directly attached to a ring, R1 is hydrogen or an aliphatic radical and n is 2 to 10 are used as antioxidants for natural rubber.  In examples the polymers are derived from 2-alkyl-4-methyl phenol, allyl-p-tolyl ether, allyl cresol, and allyl-b -naphthol.  In example 5 the use of the antioxidants in a composition comprising pale crepe rubber, zinc oxide, calcium carbonate, sulphur, hexamethylene tetramine and stearic acid is described.