| 摘要 |
Solid homogeneous mixtures of synthetic elastomeric polymers or copolymers of a conjugated aliphatic diolefine having 4 to 6 carbon atoms and inorganic fillers are prepared by dispersing the filler in an aqueous emulsion of the polymer, the emulsion containing an ion-active emulsifier, and precipitating by adding to the emulsion obtained an aqueous solution of an organic compound which contains a plurality of ionizable groups opposite in charge to that of the ionic emulsifier, and which sufficiently inactivates the emulsifier to coagulate the polymer together with the filler; the coagulation preferably is performed at a pH of between 6 and 9. Elastomeric polymers and copolymers mentioned are polymers of butadiene, chloroprene, isoprene, dimethylbutadiene and copolymers of these diene monomers with styrene, acrylonitrile and esters of acrylic and methacrylic acid with lower aliphatic saturated monohydric alcohols such as methanol, ethanol, propanol and butanol. All conventional rubber fillers may be used such as lime, chalk, magnesia, calcium silicate, aluminium silicate, but silicic acid is preferred. Either anion-active emulsifiers, e.g. a water-soluble alkali metal salt of coconut oil fatty acid, or cation-active emulsifiers of the dodecylamine type may be applied, a large number of suitable emulsifiers being specified. Suitable for the precipitation of the emulsions which contain anion-active emulsifiers are basic organic nitrogen compounds containing at least two primary and/or secondary and/or tertiary amino groups, or their quaternization products, the compounds being water-soluble as such or at least in the form of their salts with inorganic or organic acids or of their quaternization products, e.g. (a) polyalkylene polyamines, (b) polyimines, (c) polyureas, (d) acid soluble products obtained by reacting an amine containing at least two nitrogen atoms having reactive hydrogen atoms bonded to them such as ethylene diamine, propylene diamine, N-methyl propylene-diamine or polyethylene polyamines, with a resinous epoxide having an epoxide equivalent of 225 to 1,000, (e) basic condensation products containing free epoxy groups obtained by reacting a polyamine with epichlorhydrin or dichlorohydrin, (f) polyamides obtained from diprimary amines with one or several secondary or tertiary nitrogen atoms in the chain and dicarboxylic acids, polyoxamides or the basic condensation products obtained by reacting an a or b halogeno fatty acid ester with a primary or secondary polyamine, (g) polyurethanes and (h) polymers containing amino groups obtained by reacting halogen-containing polymers with amines, amino groups containing polysaccharides, or hydrolysates of protein substances; one preferred product is that obtained by adding 1 mole of epichlorhydrin at a temperature of 0 DEG to 50 DEG C. to an aqueous solution of at least 1 mole of an acylic tertiary amine having 1 to 4 carbon atoms. Polyacrylic acid salts are suitable for the precipitation of a latex prepared with a cation-active emulsifier such as a quaternary ammonium salt of dodecylamine. According to an Example (1) 100 parts of a 20% butadiene-styrene latex are mixed with 67 parts of a 15% aqueous suspension of a silicic acid rubber-filler and the latex-silicic acid mixture is precipitated at pH 8 to 9 with 3 parts (based on the rubber content) of one of the following products which are applied in the form of their water-soluble hydrochloride or acetate in 10-20% aqueous solutions: (a) polyethylene imine, (b) a condensation product of dicyandiamide, guanidine and formaldehyde, (c) a condensation product of tetramethyl ethylene diamine and 1,4-dichlorobutane to which 3 parts of common salt are added, and (d) a condensation product of dicyandiamide, guanidine hydrochloride, ammonium chloride and formaldehyde, containing 3 parts of common salt. The resulting precipitates can be easily and quickly filtered without the silicic acid separating out as a constituent. In other examples butadiene-styrene latex-silicic acid mixtures were precipitated by one of the following products, (2) sulphuric acid salt of the polyurea of g ,g 1-diaminopropyl methylamine and hexamethylene diisocyanate, (3) specific condensation products of epichlorhydrin with dimethylamine, diethylene triamine, dipropylene triamine, or g ,g 1-diaminopropyl methylamine, (4) the condensation product of 1 part of g ,g 1-diaminopropylmethylamine and 3,3 parts of epichlorhydrin, neutralized with sulphuric acid, (5) the condensation product of 1 part of g ,g 1-diaminopropylmethylamine and 3,3 parts of epichlorhydrin, neutralized with sulphuric acid, and (6) the condensation product of 1 mol. of trimethylamine and 1 mol. of epichlorhydrin. Specifications 610,311, 616,443, 706,717, 721,238, 723,767, 729,122, 763,183, 774,101, 784,946 and U.S.A. Specifications 2,772,248 and 2,849,411 are referred to. |
