Patent GB-807454-A (GB)
Title: Surface-modified silica products and silicone rubbers containing the same
Inventor: NICKERSON RALPH FRANCIS
IPC: C07F7/04
Filed: 1955-05-06
Abstract: Hydrated silica, polysilicic acid, or partially dehydrated silicic acid having an acid number, as defined, above 0.2 but below 0.85, is coated with an organic silicate having at least two alkoxy-, aryloxy-, aralkoxy-, or alkaryloxy-groups, or at least one each of two such groups and having the silicon atom thereof attached to at least one other oxygen atom, and is simultaneously, or subsequently comminuted.  The silica should contain 1000 or more silanol groups and have a surface area 80-600 sq. m./grm. and bulk density less than 10 lbs./cu. ft. The silica may be an aerogel prepared by adding aqueous sodium silicate, with stirring to aqueous sulphuric acid, and either cooling the resulting hydrosol to 50 DEG  C., adjusting the pH to 5, breaking up the resulting gel, filtering, washing and drying, or converting the resulting hydrosol to an alcohol with ethyl alcohol, centrifuging out sodium sulphate, adjusting the pH to 3.6 with aqueous sodium bicarbonate, and heating in an autoclave above the critical temperature of the alcohol-water vehicle.  The silica may be immersed in an anhydrous solution of the silicate and comminuted in an air grinding mill, or freshly prepared aerogel before removal from the autoclave may be treated with vapour of a silicate, a spray of silicate, or a spray of silicate solution and then comminuted.  Alternatively, silica aerogel undergoing comminution in an air grinding mill at 100-200 DEG  C. may be subjected to the action of silicate vapour, or a spray of silicate, or of a solution thereof.  The silica particles, carrying a coating 2-35 per cent of silicate, and comminuted to size 0.01-15 microns are hydrophilic, partially or completely hydrophobic, and non-organophilic, or organophilic depending on the amount of silicate.  The surface film appears to be a polymer of the silicate held by reaction with the silanol groups.  The properties of the coated silica are improved by ageing at room temperature, or by heating under atmospheric, or sub-atmospheric, pressure to 80-300 DEG C. for 5 mins.-24 hours.  The organic silicates are of general formula <FORM:0807454/III/1> where R are alkyl, aryl, alkaryl, or aralkyl groups and x is 1-20, e.g. tetramethyl-, tetraethyl-, tetrabutyl-, tetrapropyl-, tetrabenzyl,- or tetraphenyl-orthosilicates, or polymers thereof, or alkyl esters of tetrasilicic, metadisilicic, or metatrisilicic acids.  The coated silica may be used as a reinforcing filler for silicone rubbers, as flatting agents for lacquers or as oil thickeners.  Specifications 649,896, 654,850 and 807,453 are referred to.ALSO:Hydrated silica, polysilicic acid, or partially dehydrated silicic acid having an acid number, as defined, above 0.2 but below 0.85 is coated with an organic silicate having at least two alkoxy-, aryloxy-, aralkoxy-, or alkaryloxy-groups, or at least one each of two such groups and having the silicon atom thereof attached to at least one other oxygen atom, and is simutaneously, or subsequently, comminuted, and the coated silica may be used as a reinforcing filler for silicone rubbers. 10-55 parts coated silica are incorporated into 100 parts silicone gum in the presence of 1-6 parts benzoyl peroxide or tert.-butyl perbenzoate, and the composition is aged 5-100 days at 60-100 DEG F., remilled, and vulcanized at 110-225 DEG  C.  The silicone gum may be a dimethyl polysiloxane prepared by heating a hydrolysate of dimethyldichlorosilane in the presence of iron chloride, sodium or potassium hydroxides, or sulphuric acid or a copolymer of at least 90 per cent dimethylsiloxane and not more than 10 per cent diphenylsiloxane.  Specifications 649,896, 654,850 [both in Group III], and 807,453 are referred to.