DE1083047B - Process for the production of colored polyester resins - Google Patents

Description

Process for the production of colored polyester resins It has been found that valuable colored polyester resins are obtained by polymerizing them out of polyesters from unsaturated dicarboxylic acids, especially maleic acid, and glycols with unsaturated polymerizable compounds, especially styrene, with shaping according to a method known per se, if one before or during the polymerization isocyanate group-containing dye is added, which is free of water-solubilizing groups is.

The isocyanate group-containing dyes to be used according to the process are free from water-solubilizing groups and expediently have one to two isocyanate groups. In addition to the isocyanate groups, they can also contain substituents free of reactive groups, such as. B. halogen atoms, alkyl, alkoxy, nitro or carbalkoxy groups. Examples are anthraquinone dyes, but especially monoazo dyes. A large number of these are known and can, for example, by the method described in PB report 73919, p. 1585, by heating the chlorohydrates of the corresponding amino group-containing dyes with phosgene in an inert organic solvent, for example nitrobenzene, or by condensing 1 mol of a monoamino dye can be obtained in a simple manner with 1 mole of a diisocyanate. Dyes of the benzene-azo-benzene, benzene-azo-pyrazolone, benzene-azoacetoacetic acid arylide or benzene-azo-naphthalene series are particularly suitable. Some examples are given below: The dyes are expediently added in an inert organic solvent, for example benzene, toluene or nitrobenzene, or in one of the polycondensation or polyaddition components.

The polyaddition is carried out by the customary methods, if necessary in the presence of catalysts.

The dyed fabrics obtained according to the process, be they shaped Structures or lacquers contain the dye chemically bound. The colorations are therefore solvent-proof. The substances obtained according to the process can also, according to Conversion into a finely divided form to be used as pigments.

In the example below, the parts mean unless otherwise is indicated, parts by weight, the percentages percentages by weight, and the temperatures are given in degrees Celsius.

Example To 60 parts of an unsaturated polyester resin made from maleic acid and glycols and 40 parts of monostyrene 1 part of a 10% solution of azobenzene-4-isocyanate added in monostyrene. Then 4 parts of a 100% cobalt naphthenate solution are added and 4 parts of methyl ethyl ketone hydroperoxide, 6001, ig in dibutyl phthalate, added.

A plate with a wall thickness is cast from this mixture of about 3 mm and cured for 1 hour at 100 ".

For comparison, polyester sheets were used under the same conditions which were stained with p-acetaminoazobenzene.

The polyester plates stained with the isocyanate dyes were about 10 mouth stronger than the comparison plates.

In the table below, a number of other dyes are mentioned in column I which, when applied according to the information in this example, result in colorings that are fast to solvents and varnish and of the shade indicated in column II. 1 | II Dyes Coloring in polyurethane plastic 1 -C HIC H, NCO brown orange . X woOH \ y \ 7 2 N) N \ ½CH2CH2NCO brown orange ;); ) NCO I. 3 N - NÜYÖNCO Orange . ' NCO 7N = NM '/ NHCQHNCH3 4 / yellow orange NCO The dyes used in this example can be obtained as described below under 1 to 7 1. 35 parts of p-aminoazobenzene are dissolved in 350 parts of o-dichlorobenzene and the solution is saturated with phosgene at 0 to 5 °. With further introduction of phosgene, the temperature is increased to 110 to 1200 within 3 to 4 hours, the initially precipitated carbamic acid chloride converting into the soluble isocyanate with elimination of hydrochloric acid. After complete dissolution has occurred, the reaction mixture is evaporated to one third of the initial volume at 15 mm Hg. On cooling, the reaction product, azobenzene-4-isocyanate, separates out in crystalline form.

2. 20 parts of very finely powdered p, p'-diaminoazobenzene dihydrochloride is o-dichlorobenzene in 400 parts suspended and the solution at 0 ° with phosgene saturated.

Continuous introduction of phosgene takes place within 2 hours heated to 1200, with conversion to the isocyanate solution occurs. After expelling the phosgene with nitrogen becomes about two thirds of the o-dichlorobenzene at 15 mm Hg distilled off. On cooling, azobenzene diisocyanate (4,4 ') separates from the residue crystalline. Yield about 75010.

3. 25 parts of benzolazonaphthylamine- (1,4) are in 200 parts of toluene dissolved and precipitated as the hydrochloride at 0 ° by passing in hydrogen chloride. The solution is then saturated with phosgene at 0 ° and within 2 hours heated to boiling with constant introduction of phosgene. After about 2 hours that is Hydrochloride implemented. The vacuum is reduced to about one-third a, after which on cooling benzene-azo-naphthyl isocyanate (1,4) crystallizes out.

4. 1 part of the dye of the formula is dissolved in 15 parts of toluene and added dropwise to 15 parts of toluene saturated with phosgene at 0 ° over the course of 1 hour. The mixture is heated to 80 "over the course of 3 hours while passing in phosgene. After this time, the initially precipitated carbamic acid chloride has dissolved with formation of isocyanate. The violet-colored solution is concentrated to one fifth of its initial volume at normal pressure. The isocyanate precipitates in crystalline form by adding petroleum ether the end.

5. 1 part of the dye of the formula is finely ground, suspended in 50 parts of o-dichlorobenzene and saturated with phosgene at 0 °. With constant introduction of phosgene, the mixture is heated to 1300 over the course of 5 hours and kept at this temperature until complete dissolution occurs. By concentrating the reaction mixture at 15 mm Hg to one fifth of the original volume, the diisocyanate is obtained in crystalline form in about 850% yield.

6. 1 part of the dye of the formula is dissolved in 50 parts of o-dichlorobenzene and saturated with hydrochloric acid gas at 0 °, the dichlorohydrate precipitating finely. The excess hydrochloric acid is expelled with nitrogen and then phosgene is passed in at 0 ° until saturation. With constant introduction of phosgene, the temperature is increased to 1500 within 3 hours and held until solution has occurred. The phosgene is displaced by nitrogen and the solution is concentrated in vacuo to one tenth of the original volume. After cooling, the aliphatic-aromatic diisocyanate crystallizes out.

7. 1 part of 2,4-tolylene diisocyanate is dissolved in 10 parts of dry benzene and heated to the boil. A solution of 1 part of p-aminoazobenzene in 5 parts of benzene is added dropwise over the course of 1 hour. After the end of the dropwise addition, the mixture is refluxed for a further 1/2 hour. The yellow dye of the formula falls during the reaction and on cooling which is purified by recrystallization from acetone.

It is the reaction of saturated polyesters with isocyanate groups Dyes known, but was an analogous reaction of unsaturated polyesters not to be expected because the polymerization of unsaturated compounds such as styrene, by z. B. azo compounds is inhibited.

PATENTED DRY: 1. Process for the production of colored polyester resins by polymerizing out polyesters unsaturated dicarboxylic acids and glycols with unsaturated polymerizable compounds with shaping according to known methods Process, characterized in that one before or during the polymerization isocyanate group-containing dye is added, which is free of water-solubilizing groups is.

Claims (1)

2. The method according to claim l, characterized in that one Monoazo dye containing one to two isocyanate groups is used. Documents considered: German Auslegeschrift No. l 022788.