Patent GB-976433-A (GB)
Title: Improved lignin-reinforced rubber and method of preparation thereof
IPC: C08L9/00
Filed: 1962-02-09
Abstract: An aqueous solution containing lignin and a minor proportion of a phenolic resin resole based on the weight of lignin, and obtained by mixing solutions of the lignin and resole, is treated with an acidic material so as to effect co-precipitation of the lignin and phenolic resin resole.  The product is suitable as a reinforcing agent for natural or synthetic rubbers.  It has greater resistance to heat than lignin alone.  The resole may be used in a proportion of 0.1 to 15%, preferably 0.5 to 2% by weight of the weight of lignin.  The resole may be obtained by condensing formaldehyde, acetaldehyde, furfural, or benzaldehyde with phenol, resorcinol, cresols, or xylenols.  The lignin-phenolic resin resole product may be re-dissolved in an aqueous alkaline solution and then mixed with a rubber latex and the mixture may then be precipitated by addition of acid.  Alternatively, the mixed solutions of lignin and resole may be added directly to the latex, and the rubber, lignin, and resole may be co-precipitated. If desired a lignin which has been oxidized by blowing air through a sodium lignate solution at pH 10-11 and 160 DEG F. for 24 hours, may be used.  Specification 781,019 is referred to.ALSO:The heat resistance of a lignin-rubber coprecipitate is improved by combining the lignin to be employed in the coprecipitation process with a phenolic resin resole.  The lignin-rubber coprecipitates thus obtained may be heated, as slurries, to temperatures in the range of 180-200 DEG F. without causing serious fusion of the lignin, and the dry lignin-rubber may be heated to temperatures in excess of 300 DEG F. without reducing the reinforcing properties of the lignin in the rubbers.  The resoles used are methylol phenol compounds prepared by condensing an aldehyde with a phenolic material in the presence of an alkaline catalyst.  The lignin-rubber coprecipitates may be prepared by mixing a joint solution of lignin and a phenolic resin resole with latex and precipitating the lignin-latex-resin mixture with acid; or they may be prepared by first isolating the mixture of lignin and phenolic resin resole and then adding the mixture in the form of an aqueous alkaline solution to the latex and coprecipitating the lignin-latex-resin mixture. Rubbers specified are natural rubber butadienestyrene, chlorobutadiene and acrylonitrile rubbers.  The lignin loading of these rubbers is in the range of 25-150 parts by weight of lignin to 100 parts by weight of rubber solids.  The quantity of resole employed may be from 0.1-15%, preferably 0.5 to 2%, by weight of the weight of lignin.  In an example, a solution of kraft pine sodium lignate is mixed with a phenol-formaldehyde resole solution in water and then a butadiene styrene latex is added.  The mixture is then precipitated by adding hot dilute sulphuric acid. The resulting slurry is heated by injection of steam and then filtered, and the filter-cake is washed and dried.  Zinc oxide, stearic acid, and a coal tar plasticizer are added.  Vulcanizers are added and the composition is heat cured. Other examples are given. The lignin used may be a lignin which has been subjected to oxidation to render it resistant to heat.  Specification 781,019 is referred to.