Patent GB-1087906-A (GB)
Title: Glass fibre-elastomer assembly with sulphur-containing anchoring agents
IPC: C08K3/16
Filed: 1963-12-05
Abstract: An elastomer is bonded to glass fibres through an anchoring agent that is an organo-metallic co-ordination-complex compound containing at least one thio group or an organo-silicon compound containing at least one thio group.  The anchoring agent is first applied to the surfaces of the glass fibres, and the fibres are thereafter combined with the elastomer in an uncured or partly cured condition.  The elastomer is one which, at least before it is fully cured, contains olefinic groups or halogen substituents or both, e.g. neoprene, chlorbutyl rubber, or natural rubber containing resinous acids, or is a polyurethane. The term "glass fibres" includes continuous filaments formed by attenuation from molten streams of glass, staple fibres formed by attenuation of molten streams of glass by blasts of air or steam, strands, yarns or fabrics formed of such filaments or staple, and thin flexible glass flakes.  The anchoring agent may be included in the size applied to the fibres during formation or may be applied thereto subsequently, e.g. by impregnation, or may be included in the elastomeric material.  The anchoring agent may act as a curing or hardening agent for the elastomeric material.  Organic compounds specifically referred to as anchoring agents include thiopropyl-triethoxy-silane, thio-methyl - trichlor - silane, thiotoluyl - diethoxy-silane, thiopropyl - trimethoxy - silane, g  - thio-propyl - triethoxy - silane, thioethyl - dichloro - silane, thiobutyl - triethoxy - silane, thio-phenyl - diethoxy - silane and Werner complex compounds such as thioacetato-chrome complex, thiomethacrylato-chrome complex and thiobenzoato-chrome complex. Organos-silanes containing a thiol group are made as follows: (Example 1) hydrogen sulphide is bubbled through an alkenyl-triethoxysilane in the presence of a clay catalyst at 100 DEG C. at 5 atmospheres pressure; (Example 2) 3-chloropropyl - trichlorosilane is reacted with hydrogen sulphide in the presence of alcoholic KOH at 125 DEG  F. and 100 p.s.i.; similar reactions can be carried out with chloroethyl-, chlorobutyl-or bromoethyl-silicon trichloride; (Example 3) an epoxyalkyl-triethoxysilane is reacted with hydrogen sulphide under pressure: (Example 4) two molecules of an epoxyalkylsilane react with one of hydrogen sulphide to form a dimer containing one epoxy group and one thiol group in the molecule; and (Example 5) a dimer containing two epoxy groups reacts with hydrogen sulphide to yield the same dimer as in Example 4.  Reference is also made to the formation of a Grignard reagent by reaction of gamma-chloro-propyl-triethoxysilane with magnesium in the presence of ethyl ether, followed by the reaction of the resulting compound with sulphur, and to the reaction of gamma-chloro-propyl-triethoxy-silane with thiourea in the presence of sodium carbonate.  Compositions comprise: (Example 8) thiomethyl - trichlorosilane, glycerine and water; (Example 10) the product of Example 4, ethylene glycol and water; (Example 12) dextrinized starch, hydrogenated soya oil, laurylamine acetate, non-ionic emulsifying agent and thiopropyl-trimethoxy -silane; (Example 13) polyester resin, stearylamine chloride, tetraethylene-pentamine-stearic acid condensate solubilized with acetic acid, polyvinyl alcohol, polyvinyl-pyrrolidone, gamma - thiopropyl - triethoxy - silane, acetic acid and water; and (Example 18) the product of Example 4, rubber and sulphur, with or without additional filler.  The rubber in this last example may be natural rubber, neoprene, isoprene or butadiene polymers or copolymers.ALSO:An elastomer is bonded to glass fibres through an anchoring agent that is an organometallic coordination-complex compound containing at least one thio group or an organosilicon compound containing at least one thio group.  The anchoring agent is first applied to the surfaces of the glass fibres, and the fibres are thereafter combined with the elastomer in a uncured or partly cured condition.  The elastomer is one which, at least before it is fully cured, contains olefinic groups or halogen substituents or both, e.g. natural rubber, neoprene, isoprene or butadiene polymers or copolymers, or is a polyurethane.  The term "glass fibres" includes continuous filaments formed by attenuation from molten streams of glass, staple fibres formed by attenuation of molten streams of glass by blasts of air or steam, strands, yarns or fabrics formed of such filaments or staple, and thin flexible glass flakes.  The anchoring agent may be included in the size applied to the fibres during formation or may be applied thereto subsequently, e.g. by impregnation, or may be included in the elastomeric material. The anchoring agent may act as a curing or hardening agent for the elastomeric material.  Organic compounds specifically referred to as anchoring agents include thiopropyltriethoxy - silane, thiomethyl - trichloro-silane, thiotoluyl-diothoxy-silane, thiopropyl-trimethoxy-silane, g -thiopropyl-triethoxy-silane, thioethyl-dichloro-silane, thiobutyltriethoxy-silane, thiophenyl-diethoxy-silane and Werner complex compounds such as thioacetato-chrome complex, thiomethacrylatechrome complex and thiobenzoato-chrome complex.