RU2069680C1 - Method for production of oligomer dyes - Google Patents

Abstract

FIELD: production of oligomer dyes. SUBSTANCE: method is carried out by interaction of aromatic epoxy resins with monobasic carboxylic acids and with dyes, mass ratio of said ingredients being 1:0.06-0.20:0.08-0.37 respectively. Molecular weight of mentioned above epoxy resins is 600-4500 g/mol. Mentioned above monobasic carboxylic acids are used as modifying agents and said dyes contain carboxyl and/or sulfamide groups. EFFECT: improves efficiency of the method. 1 tbl

Description

 The invention relates to the field of organic dyes, in particular to polymer-soluble dyes containing polymer fragments in the molecule, i.e., oligomeric dyes, and a method for their preparation.

 It is known [1] to obtain structurally colored polymers in which the dye is covalently bonded to the polymer by copolymerization (or condensation) of monomers with dyes containing groups such as vinyl, hydroxy, amino and others, with the formation of polymer (oligomeric) chains. The main disadvantages of this method of obtaining colored materials are that the polymers are painted at the stage of their synthesis. At the same time, the introduction of a significant amount of the chromophore part dramatically changes the properties of polymers and, no less important, requires the creation of special dyes for each type of polymer.

 We found that dyes containing oligomeric fragments of a certain structure and chain length are able to color various polymers at the stage of their processing. The main advantage of such oligomeric dyes is that they color the polymer material, dissolving in the substrate to be coated, i.e. homogenously. Therefore, when using them, unlike pigments, there is no need for thorough dispersion, maximum coloring power is achieved and the physical and mechanical strength of colored polymers is maintained.

Closest to the proposed method for the combination of essential features is a method consisting in the condensation of biophenol and epichlorohydrin in the presence of 0.1 to 5 wt. to epichlorohydrin of 1- (2,3-epoxypropyl) aminoanthraquinone or 1,4-bis (2,3-epoxypropyl) aminoanthraquinone at 40 65 ^o C followed by the addition of an aqueous solution of caustic soda, heating to 70 75 ^o C and further necessary treatments ( extraction, washing, drying) [2]
This method has a number of significant drawbacks, such as multi-stage, the use and isolation of toxic products, the need for washing by-products and, accordingly, disposal or liquidation of effluents, the use of deficient aminoanthraquinones as initial dyes, in the form of their N-substituted, containing epoxypropyl groups, the introduction of which, firstly, as a rule, reduces light resistance and, secondly, causes the ambiguity of the reactions in the main process, since the interaction occurs not only on epoxy groups, but also on the nitrogen atom of the secondary amino group. The latter sharply negatively affects the coloristic properties of the dyes and makes it difficult to achieve the constancy of their color characteristics, which, in principle, makes it inappropriate to use dyes for this purpose, in which the functionally substituted amino group is directly in the chromophore system. And finally, the opposed method aims at obtaining a structurally colored polymer material in the process of its production, and not polymer-soluble dyes suitable for coloring various polymers.

 The objective of the invention is a method for producing oligomeric dyes capable of dissolving and dyeing a wide range of industrial polymeric materials (polyolefins, polyvinyl chloride, polystyrene, polyacrylates, etc.), yielding colors with high coloristic indicators, including light and migration resistance.

 The problem was solved in that epoxy compounds interact with dyes and colorless modifier compounds containing functional groups that uniquely and quantitatively react with epoxy groups.

 As epoxy compounds use industrial epoxy resins of various molecular weights.

 As dyes, dyes of various chemical classes containing carboxyl and / or sulfamide groups are used, moreover, the carboxyl group is introduced, as a rule, in the synthesis of the chromophore with the initial intermediate products, and the sulfamide group can be introduced into the finished dyes by known methods [2] that significantly expands the base of suitable dyes and is an additional advantage of the method.

 As a modifier, compounds containing functional groups capable of quantitatively reacting with epoxy compounds, including sulfamides. It is most convenient to use monocarboxylic acids of aliphatic, aromatic or heterocyclic series.

 The specified components epoxy resin, modifier and dye are introduced into the reaction at mass ratios of 1 0.06 0.20 0.08 0.37, respectively. In this case, oligomeric dyes of the following general formula are obtained.

где: K_p остаток органического красителя;
X SO₂NY-, -COO-;
Y H, алкил-, циклоалкил, арил-;
М алкил-, алкенил-, арил-, гетерил-, или К_р;
n 2 12;
m 1 4.

where: K _{p the} remainder of the organic dye;
X SO ₂ NY-, -COO-;
YH, alkyl, cycloalkyl, aryl;
M alkyl, alkenyl, aryl, heteryl, or K _p ;
n 2 12;
m 1 4.

 The process proceeds quantitatively, without isolation of any by-products.

 Example 1. Obtaining an oligomeric dye.

In a flask with a stirrer, a thermometer, a reflux condenser and a tube for supplying nitrogen, 1 wt.h. aromatic epoxy resin brand E-44 (epoxy number 5.7), heated until melted and introduced with stirring 0.20 wt. including modifier (table, example 1). Raise the temperature to 180 ^o C and mix to a residual acid value of 1 to 3 mg / g KOH. The epoxy number of the resulting epoxy ester is determined (2.5 3.0).

Powdered dye N 1 (table) is added to the molten mass in an amount of 0.21 parts by weight. The reaction mass is heated to a temperature of 185 ^o C and stirred under a stream of nitrogen. The end of the reaction is determined by the disappearance of the initial dye in the reaction mass by TLC on a Silufol plate (eluent is a 10: 1 benzene acetone mixture).

 The characteristics of the synthesized oligomeric dyes are given in the table.

 Oligomeric dyes are used for dyeing various polymeric materials, for example, polystyrene, polyacrylates, polyethylene, polyvinyl chloride, fiberglass based on epoxy resins, rubber, etc.

Claims (1)

 A method of producing oligomeric dyes by reacting epoxy compounds with dyes containing reactive groups, characterized in that aromatic epoxy resins with mol. m. 1000 4500 g / mol, monobasic carboxylic acids as modifiers, and dyes containing carboxyl and / or sulfamide groups at mass ratios of 1 0.06 0.20 0.08 0.37, respectively.

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