Sulfonyl-bridged perinones

Abstract

The invention relates to sulfonyl-bridged perinones in the form of compounds of the general formula (I) or isomeric forms thereof

##STR00001## in which R is C.sub.1-C.sub.6-alkyl, halogen, nitro, aryl, aryloxysulfonyl, hydroxy, C.sub.1-C.sub.6-alkoxy, aryloxy, optionally alkyl- or acyl-substituted amino, optionally alkyl- or aryl-substituted aminosulfonyl, or a fused-on cycloaliphatic or heterocyclic radical, to a process for production thereof and to the use thereof for bulk colouring of plastics.

Claims

1. A sulfonyl-bridged perinone of the general formula (I) or isomeric forms thereof ##STR00012## wherein R is C.sub.1-C.sub.6-alkyl, aryl, optionally alkyl- or acyl-substituted amino, optionally alkyl- or aryl-substituted aminosulfonyl, or a fused-on cycloaliphatic or heterocyclic radical.

2. The sulfonyl-bridged perinone according to claim 1, wherein R is a radical ##STR00013##

3. The sulfonyl-bridged perinone according to claim 1, wherein at least one of the phenyl rings has at least one of the substituents selected from the group consisting of chlorine, bromine, nitro, methoxy, NH.sub.2, benzyloxy, hydroxy, SO.sub.2O(C.sub.6H.sub.5), SO.sub.2N(CH.sub.3).sub.2, SO.sub.2NHCH.sub.3, methyl, ethyl, n-propyl, isopropyl, n-, sec-, tert-butyl, NHCOCH.sub.3, N(C.sub.2H.sub.5).sub.2 and phenyl.

4. The sulfonyl-bridged perinone according to claim 1, wherein formula (I) is 10,10-sulfonylbis-12H-phthaloperin-12-one.

5. The sulfonyl-bridged perinone according to claim 1, having a colour distance E<20 of the L*a*b* coordinates from a colour number beginning with 3 in the RAL colour chart for the colour red.

6. The sulfonyl-bridged perinone according to claim 5, having a yellow tinge where a*>0 and b*25.

7. A method of bulk colouring plastic comprising dissolving a sulfonyl-bridged perinone of the formula (I) or isomeric forms thereof ##STR00014## wherein R is C.sub.1-C.sub.6-alkyl, halogen, nitro, aryl, aryloxysulfonyl, hydroxy, C.sub.1-C.sub.6-alkoxy, aryloxy, optionally alkyl- or acyl-substituted amino, optionally alkyl- or aryl-substituted aminosulfonyl, or a fused-on cycloaliphatic or heterocyclic radical in the plastic.

8. The method according to claim 7, wherein at least one of the phenyl rings in formula (I) has at least one of the substituents from the group consisting of chlorine, bromine, nitro, methoxy, NH.sub.2, benzyloxy, hydroxy, SO.sub.2O(C.sub.6H.sub.5), SO.sub.2N(CH.sub.3).sub.2, SO.sub.2NHCH.sub.3, methyl, ethyl, n-propyl, isopropyl, n-, sec-, tert-butyl, NHCOCH.sub.3, N(C.sub.2H.sub.5).sub.2 and phenyl.

9. The method according to claim 7, wherein in formula (I) the sulfonyl bridge is disubstituted by the same radicals.

10. The method according to claim 9, wherein in formula (I) the sulfonyl bridge bridges the same two 12H-phthaloperin-12-one radicals to one another.

11. The method according to claim 10, wherein formula (I) is 10,10-sulfonylbis-12H-phthaloperin-12-one.

12. The method according to claim 7, wherein the plastic is a thermoplastic for extrusion, a thermoplastic for blow moulding or a thermoplastic for injection moulding.

13. The method according to claim 12, wherein the plastic is a vinyl polymer, a polyester, a polyolefin or a polyamide.

14. The method according to claim 13, wherein the polyolefin is selected from polyethylene or polypropylene, the vinyl polymer is selected from polystyrene, a styrene-acrylonitrile copolymer, a styrene-butadiene copolymer, a styrene-butadiene-acrylonitrile terpolymer, polymethacrylate or polyvinylchloride, the polyester is selected from polyethylene terephthalate, polybutylene terephthalate, polycarbonate or cellulose ester, and the polyamide is selected from nylon-6 or nylon-6,6.

15. The method according to claim 7, wherein at the same time, migration characteristics in the plastic, determinable according to DIN 53775-3, are reduced.

16. The method according to claim 7, wherein at the same time, the thermal stability of dyes in the plastic, determinable according to DIN EN 12877, is increased.

17. A process for the production of sulfonyl-bridged perinones of the formula (I) or isomeric forms thereof ##STR00015## wherein R is C.sub.1-C.sub.6-alkyl, halogen, nitro, aryl, aryloxysulfonyl, hydroxy, C.sub.1-C.sub.6-alkoxy, aryloxy, optionally alkyl- or acyl-substituted amino, optionally alkyl- or aryl-substituted aminosulfonyl, or a fused-on cycloaliphatic or heterocyclic radical, comprising reacting sulfonyl-substituted isobenzofurandiones with at least one aromatic diamine from the group of naphthylene-1,8-diamine, chloronaphthylene-1,8-diamine, dichloronaphthylene-1,8-diamine, methylnaphthylene-1,8-diamine, dimethylnaphthylene-1,8-diamine, methoxynaphthylene-1,8-diamine, ethoxynaphthylene-1,8-diamine, acetaminonaphthylene-1,8-diamine and 1,8-diaminoacenaphthylene.

18. An extruded, blow-moulded or injection-moulded product comprising at least one sulfonyl-bridged perinone of the general formula (I) or isomers thereof ##STR00016## wherein R is C.sub.1-C.sub.6-alkyl, halogen, nitro, aryl, aryloxysulfonyl, hydroxy, C.sub.1-C.sub.6-alkoxy, aryloxy, optionally alkyl- or acyl-substituted amino, optionally alkyl- or aryl-substituted aminosulfonyl, or a fused-on cycloaliphatic or heterocyclic radical, and at least one plastic.

19. The extruded, blow-moulded or injection-moulded product according to claim 18, wherein the plastic is at least one thermoplastic.

20. The extruded, blow-moulded or injection-moulded product according to claim 18, wherein the at least one plastic is selected from the group consisting of vinyl polymers, polyesters, polyolefins and polyamides.

Description

EXAMPLES

Example 1

[0070] 63 g of phenol was melted at a temperature of 80 C. To this was added 5.27 g (32.7 mmol) of 1,8-diaminonaphthalene, and the mixture was stirred for 30 minutes. Subsequently, 6.32 g (16.8 mmol) of 5,5-sulfonylbis(isobenzofuran-1,3-dione) was introduced. This reaction mixture was heated to 135 C. and kept at that temperature for 6 hours, and the resultant water of reaction was distilled off. The reaction mixture was then cooled down to 100 C. within 1.5 h, and 65 g of methanol was added. The reaction mixture was stirred for a further 10 hours and cooled down to 30 C. The reaction product was isolated using a suction filter and washed first with 40 g of methanol and then washed with 400 g of water. After drying in a vacuum drying cabinet at 80 C. and 150 mbar, an isomer mixture comprising essentially 10,10-sulfonylbis-12H-phthaloperin-12-one of formula (II) was obtained in a yield of 99% with red colour close to RAL 3028.

##STR00010## ##STR00011##

[0071] The formula (II) of the sulfonyl-bridged 10,10-sulfonylbis-12H-phthaloperin-12-one dye as shown in the reaction scheme represents only one form of possible isomers that can arise in the synthesis.

[0072] By way of evidence of the improvements in the properties described in the description, corresponding polymer compositions were first produced by compounding from polycarbonate (polymer composition 1) and from nylon-6 (polymer composition 2) with 10,10-sulfonylbis-12H-phthaloperin-12-one and its isomers. To this end, the individual components were mixed in a twin-screw extruder (Leistritz LSM 30-34 from Leistritz AG (Nuremberg, Germany)) at temperatures between 240 C. and 260 C., extruded, cooled until pelletizable and pelletized. After drying (generally for two days at 80 C. in a vacuum drying cabinet), the pellets were processed by injection moulding at temperatures in the range from 240 to 300 C. to give standard test specimens for the respective tests.

[0073] In the context of the present invention, migration of the 10,10-sulfonylbis-12H-phthaloperin-12-one and its isomers was examined using plaques of dimensions 60.Math.40.Math.2 mm.sup.3 based on the thermoplastics polycarbonate and nylon-6 according to standard DIN 53775-3. This was done by clamping the test specimen dyed with the sulfonyl-bridged perinone having the empirical formula C.sub.36H.sub.18N.sub.4O.sub.4S between two uncoloured test specimens having a pressure of 4 N/cm.sup.2 at a temperature of 80 C. for 24 h and then visually assessing migration based on dye residues on the test specimens that were initially colourless.

[0074] Likewise in the context of the present invention, the thermal stability of the moulding compounds described in Tab. I that had been coloured with 10,10-sulfonylbis-12H-phthaloperin-12-one and its isomers was assessed by means of the 60.Math.40.Math.2 mm.sup.3 plaques, in accordance with standard DIN EN 12877.

[0075] Component A): polycarbonate (Makrolon 2800, from Covestro AG, Germany)

[0076] Component B): nylon-6 (Durethan B30S, from Lanxess Deutschland GmbH, Cologne, Germany)

[0077] Component C): isomers of 10,10-sulfonylbis-12H-phthaloperin-12-one according to Example 1

TABLE-US-00002 TABLE 2 Polymer Polymer composition 1 composition 2 Component A) parts by mass 99.8 Component B) parts by mass 99.8 Component C) parts by mass 0.2 0.2 Migration none apparent none apparent Thermal stability C. 350 280

[0078] The results in Tab. 2, for 10,10-sulfonylbis-12H-phthaloperin-12-one and its isomers, do not show any apparent migration thereof into or out of polymer compositions 1 and 2, and the polymer plaques based on 10,10-sulfonylbis-12H-phthaloperin-12-one and its isomers, and also polycarbonate and nylon-6, are notable for very high thermal stability that extended up to the processing limits of the polymer compositions examined.

[0079] It will be understood that the specification and examples are illustrative but not limitative of the present invention and that other embodiments within the spirit and scope of the invention will suggest themselves to those skilled in the art.