Patent GB-807911-A (GB)
Title: Improvements in or relating to reinforcing fillers for rubbery materials and to rubbery compositions containing the same
IPC: C08K9/04
Filed: 1955-05-19
Abstract: A particulate, solid, inorganic oxygen and silicon-containing compound, e.g. fibrous or spherical silicon monoxide, silicon oxyimide, fibrous arc or fume silica, has a surface coating of at least one polyhydroxy organic compound in which the OH radicals are linked to each other through C atoms only, applied thereto in amount sufficient to impart increased abrasion resistance and flexibility to rubbery materials in which it is used as a reinforcing filler.  2 1/2 -30 per cent polyhydroxy compound may be applied by spraying, mixing, dipping, or vaporization, and the silicon compound may be densified before, during or after coating by treatment with ethanol, or ball milling, or heating at 150-300  DEG  C., and should be size 5-600 mm .  The polyhydroxy compound may be of general formula X[-R-](OH)N, where R is a saturated or ethylenically unsaturated hydrocarbon radical containing at least 2 C atoms, N is at least 2, and X is H, alkyl, alkenyl, aryl, R1COO, or R1O, where R1 is H, alkyl, alkenyl, or polyenyl.  Halogen substituted derivatives may be used.  Examples are trimethylol propane; phenyl trimethylol methane; 1,1,1-trimethylol-2,4,4-trimethyl pentane; 2,2-diethyl propanediol-1,3; 2 - ethyl - 2 - butyl propanediol - 1,3; 1,1,1 - trimethylol hexane; pentaerythritol mono-oleate; glyceryl monoricinoleate; and glyceryl monolaurate.  The coated silicon compound is used in amount 15-45 per cent as reinforcing filler. The compound may be milled into the composition or mixed with latex, which is coagulated and dried, and the composition may include accelerator, vulcanizing and antioxidant ingredients. The rubber may be natural rubber, e.g. balata, or gutta percha, polychloroprene, polymers of conjugated dienes, e.g. butadiene-1,3, isoprene, 2,3- or 1,4-dimethyl butadiene-1,3, copolymers of such dienes, or containing at least 50 per cent conjugated diene with iso-butylene, methyl or ethyl acrylates or methacrylates, 2-vinyl pyridine, styrene, acrylo- or methacrylonitriles, or mixtures of these, or polyacrylic rubbers obtained by polymerization of esters of acrylic acid, e.g. methyl, ethyl or butyl acrylates, or mixtures thereof, or by copolymerization of acrylic esters with 5-10 per cent chloroethyl vinyl ether, acrylonitrile, vinyl chloride, dichlorodifluoroethylene, or styrene. The acrylic rubbers may be mixed with 80-20 parts polychloroprene, butadiene-1,3, styrene copolymers or natural rubber.  In examples (I)-(V) a composition of natural rubber, zinc oxide, stearic acid, pine tar, phenyl-b -naphthylamine, 2-mercaptobenzothiazyl disulphide, sulphur and didodecylamine is milled with fibrous silicon monoxide, are silica, or silicon oxyimide, which have been coated with one or other of the specified polyhydroxy compounds in ethanol solution or as vapour, with or without a densification by ball milling, heat, heating in water vapour, and treating with ethanol.  Also in Example (V) coated fibrous silicon monoxide is milled into a mixture of GR-S rubber, zinc oxide, stearic acid, phenyl - b  - naphthylamine, sulphur, secondary coco amine, N-hexyl-2-mercapto benzothiazyl sulphene amide.  Specifications 804,992, 804,993, [Group IV (a)], and 804,994 are referred to.ALSO:A particulate solid, inorganic oxygen and silicon-containing compound, e.g. fibrous or spherical silicon monoxide, silicon oxyimide, fibrous, arc, or fume silica, has a surface coating of at least one polyhydroxy organic compound, in which the OH radicals are linked to each other through C atoms only, applied thereto in amount sufficient to impart increased abrasion resistance and flexibility to rubbery materials in which it is used as a reinforcing filler.  2 1/2 -30 per cent polyhydroxy compound may be applied by spraying, mixing, dipping or vaporization, and the silicon compound may be densified before, during, or after coating by treatment with ethanol, or ball milling, or heating at 150-300 DEG C., and should be size 5-600 mm .  The polyhydroxy compound may be of general formula X[R](OH)N, where R is a saturated or ethylenically unsaturated hydrocarbon radical containing at least 2 C atoms, N is at least 2, and X is H, alkyl, alkenyl, aryl, R1COO, or R1O, where R1 is H, alkyl, alkenyl, or polyenyl. Halogen-substituted derivatives may be used.  Examples are trimethylol propane, phenyl trimethylol methane, 1,1,1-trimethylol-2,4,4-trimethyl pentane, 2,2 - diethyl propanediol-1,3,2 - ethyl - 2 - butyl propanediol - 1,3,1,1,1-trimethylol hexane, pentaerythritol monooleate, glyceryl monoricinoleate, and glyceryl monolaurate.  The coated silicon compound is used in amount 15-45 per cent as reinforcing filler.  The compound may be milled into the composition or mixed with latex, which is coagulated and dried, and the composition may include accelerator, vulcanizing and antioxidant ingredients. The rubber may be natural rubber, e.g. balata, or gutta percha, polychloroprene, polymers of conjugated dienes, e.g. butadiene-1,3, isoprene, 2,-, 3- or 1,4-dimethyl butadiene-1,3, copolymers of such dienes, or containing at least 50 per cent conjugated diene with isobutylene, methyl or ethyl acrylates or methacrylates, 2-vinyl pyridine, styrene, acrylo- or methacrylonitriles, or mixtures of these, or polyacrylic rubbers obtained by polymerization of esters of acrylic acid, e.g. methyl, ethyl or butyl acrylates, or mixtures thereof, or by copolymerization of acrylic esters with 5-10 per cent chloroethyl vinyl ether, acrylonitrile, vinyl chloride, d dichlorodifluoroethylene, or styrene.  The acrylic rubbers may be mixed with 80-20 parts polychloroprene, butadiene-1,3, styrene copolymers or natural rubber.  In Examples I-V a composition of natural rubber, zinc oxide, stearic acid, pine tar, phenyl-b -naphthylamine, 2-mercaptobenzothiazyl disulphide, sulphur and didodecylamine is milled with fibrous silicon monoxide, arc silica, or silicon oxyimide, which have been coated with one or other of the specified polyhydroxy compounds in ethanol solution or as vapour, with or without a densification by ball milling, heat, heating in water vapour, and treating with ethanol.  Also in Example V coated fibrous silicon monoxide is milled into a mixture of GR-S rubber, zinc oxide, stearic acid, phenyl-b -naphthylamine, sulphur, secondary coco amine, N-hexyl-2-mercapto benzothiazyl sulphene amide. Specifications 804,992, 804,993 and 804,994 are referred to.