DE889977C - Process for coloring plastics that are soluble in organic solvents - Google Patents

Description

Process for coloring plastics which are soluble in organic solvents It is known that plastics which are soluble in organic solvents, such as the ethers and esters of cellulose and polymerization products of unsaturated Hydrocarbons and the like, such as structures made of polystyrene and polyvinyl chloride and Polymerization compounds of the acrylic acid group, generally not with acidic ones Can color dyes.

It has now been found that plastics of the type indicated above can be used make it suitable for the absorption of acid dyes, i.e. animalize them, if they are insoluble or sparingly soluble in water, but in organic solvents incorporated soluble acyl derivatives of polyalkylene polyamines. Polyalkylene polyamines It is known that the aliphatic compounds are formed in the reaction of polyhalogen compounds Series that contain further substituents, in particular oxygen-containing groups can, with ammonia "and amines, or by polymerization of alkylenimines. As Acyl derivatives come into consideration in which the acyl radical is the remainder of carboxylic acids, Sulphonic acids, also of urea and thiourea.

As acyl derivatives of polyalkylene polyamines of the present type be for example the sales products of benzoyl chloride, benzene sulfochloride, Phenyl isocyanate, butyl isocyanate, phenyl mustard oil with polyethylene polyamines and with the products of action from dihalohydrins to ammonia, diethylenetriamine and called triethylenetetramine or with polyethyleneimine. Their manufacture is not Subject of the present invention.

Because the acyl bodies present in the deformation the plastics used are soluble in organic solvents, it is possible to completely incorporate the acyl bodies in the plastic and thereby a uniform coloring of the synthetic fiber or the film with acid dyes to reach. Example i To a solution of 45 parts of a polyethylene polyamide mixture, in which the at rö mm pressure. parts passing over up to 22o ° have been removed beforehand, In about 2,000 parts of water, after adding 170 parts of sodium bicarbonate, it is left a solution of 140 parts of benzoyl chloride in about 300 parts of acetone within 2 Hours flow in, whereby the temperature should not rise above about 30 °: That The condensation product gradually separates out as a viscous mass. After iobis 2 hours After stirring, the benzoylation product has completely precipitated. It comes with water washed and dissolved in chloroform. The solution is dried with sodium sulfate and the solvent is distilled off in vacuo at 5o to 6o °. It remains a pale yellow-brown colored resin that softens at about 78 ° and in most organic Solvents is soluble.

Films or yarns made from polyacrylonitrile or polyvinyl chloride or post-chlorinated Polyvinyl chloride or a copolymer vinyl chloride + vinyl acetate, which about 5% of the above benzoylation product are added, can be with acidic Dyeing wool dyes. So z. B. Supianol brilliant blue G (Schultz, color tables, 7th ed. Vol. II, p. 265), from acidic liquor in the ratio of 2 parts to zoo parts Dyed well, a strong blue color. Example 2 For a solution of 45- Parts of a polyethylene polyamine mixture (see Example i) in about 1,000 parts of water after adding 40 parts of caustic soda, a solution of 176 parts of benzenesulfonyl chloride in about 300 parts of acetone flow in without cooling. After stirring for about two hours, stirring is continued at about 80 to about 6 hours and, after cooling, the precipitated benzenesulfoamino compound is filtered off with suction, washed and dried. It can be purified by dissolving it from chloroform and stops hard resin; which at 7i ° turns into a tough, strongly stringy mass. It is soluble in most organic solvents.

Films or yarns made of polyacrylonitrile or polystyrene, which are 5% of the above condensation product are added, result with Walkgelb H5 G (Schultz, Dye tables, 7th edition, Vol. II, p. 275), from acidic liquor in 2% strength colored, a strong yellow color. Example 3 To a solution of 45 parts of a polyethylene polyamine mixture (cf. Example i) in about 250 parts of chloroform is left with strong cooling for 70 Parts of phenyl isocyanate, dissolved in about 150 parts of chloroform, flow in. After several hours Standing at 2o to 30 °, the solution is heated under reflux for a further 2 hours and distilled the chloroform either in vacuo or with steam. You get one like that almost colorless resin that softens at go ° and is soluble in organic solvents.

Films or fibers made from polyacrylonitrile or from acetate silk, which 30 / o of the above condensation product are added, can be with acidic wool dyes to dye. For example, Wall-, rot 6BA (Schultz, Farbstofftabellen, 7th ed. Vol. II, p. 275), dyed in 3% strength from acidic liquor, a strong red color. Example 4 As in Example 3, 45 parts of a polyethylene polyamine mixture are used condensed with 6o parts of n-butyl isocyanate. It becomes tough and strong at 20 ° stringy resin obtained.

Acid wool dyes have a strong affinity for films or fibers made of polyvinyl chloride or of polystyrene to which 3% of the above condensation product has been added. For example, alizarin cyanine green 5 G (Schultz, Farbstofftabellen, 7th edition, Vol. II, p. Izi), dyed in an acidic liquor at 2.5% strength, produces a strong green color. EXAMPLE 5 45 parts of a polyethylene polyamine mixture, dissolved in about 250 parts of chloroform, are condensed with 80 parts of phenyl mustard oil with strong cooling. After standing for several hours at room temperature and refluxing for one hour, the solution is distilled with steam, leaving a resin that softens at about 76 °. It dissolves in chloroform and acetone. Its solutions can be mixed with solutions of polyacrylonitrile or polyvinyl chloride. These mixtures can be spun into fibers. Acid wool dyes have a strong affinity for fibers treated in this way. EXAMPLE 6 75 parts of the polyalkylenepolyamine, prepared for example according to the instructions of Swiss patent 170 085 by condensation of ammonia with glycerol dichlorohydrin, are treated in aqueous solution in the presence of excess sodium bicarbonate with 140 parts of benzoyl chloride, as described in Example i. The viscous resin thus obtainable is soluble in chloroform, acetone, dimethylformamide, etc. and can thus be incorporated into polyacrylonitrile fibers. A yarn produced in this way, which contains 5% of the abovementioned condensation product, can be dyed well in an acidic liquor, for example with Supranolbrillarite blue G (Schultz, Dyestuff Tables, loc. Cit.). EXAMPLE 7 52 parts of diethylenetriamine are dissolved in about zoo parts of water and condensed with 65 parts of glycerol dichlorohydrin first at room temperature and then for several hours on the water bath. The solution is made alkaline with caustic soda and, after the addition of excess sodium bicarbonate, condensed with 140 parts of benzoyl chloride. The viscous, sticky resin obtained in this way, when dissolved in organic solvents and incorporated into a polyacrylonitrile film, causes animalization. A film of this type, which contains zo% of the above condensation product, is colored strongly blue, for example, with Supranol Brilliant Blue G (aa 0.). Example 8 73 parts of triethylenetetramine are condensed in an aqueous solution with 65 parts of glycerol dichlorohydrin. The polyalkylenepolyamine thus obtainable is condensed with benzoyl chloride in an aqueous solution in the presence of excess sodium bicarbonate. In this way, a resin that is splinter-hard at 20 ° is obtained, which turns into a tough, stringy mass at 58 °. A polyacrylonitrile film containing zo% of the above condensation product is strongly colored with milled red 6BA (aa 0.) or with Supranol Brilliant Blue G (aa 0.).

Use the equivalent amount of benzene sulfochloride instead of benzoyl chloride If used in a caustic solution, a benzenesulfamino compound (softening point 90 °) obtained, which, incorporated into a polyacrylonitrile film, also strong animalization causes.

Claims (1)

PATENT CLAIM: Process for dyeing in organic solvents Soluble plastics, characterized in that these plastics are in water insoluble or sparingly soluble acyl derivatives, but soluble in organic solvents incorporated by polyalkylenepolyamines and then dyed with acidic dyes.