USE OF PHOSPHOROUS-CONTAINING ORGANIC OXYIMIDES AS FLAME RETARDANTS AND/OR AS STABILIZERS FOR PLASTICS, FLAME-RETARDANT AND/OR STABILIZED PLASTIC COMPOSITIONS, METHOD FOR THE PRODUCTION THEREOF, MOULDED PART, PAINT AND COATINGS

Abstract

The present invention relates to the use of phosphorous-containing organic oxyimides according to the general formula (I) as flame retardant for plastic materials, as radical generators in plastic materials and/or stabilisers for plastics. In addition, the present invention relates to a flame-retardant plastic material moulding compound in which the previously described phosphorous-containing organic oxyimides are integrated, and also to a method for the production of the previously mentioned plastic material composition. Furthermore, the present invention relates to a moulded article, a paint or a coating from the previously mentioned flame-retardant plastic material composition.

Claims

1-22. (canceled)

23. A method of imparting flame retardancy, stability, and/or oxidation resistance to a plastic material comprising incorporating into the plastic material an organic oxyimide containing at least one structural element of Formula I ##STR00042## wherein R.sup.1 is selected from the group consisting of phosphorus-containing radicals.

24. The method according to claim 23, wherein R.sup.1 is selected from the group consisting of
—X—Y wherein X is a direct chemical bond, an unsubstituted or substituted alkylene radical, an unsubstituted or substituted cycloalkylene radical, an unsubstituted or substituted aryl radical, an unsubstituted or substituted heteroaryl radical or an acyl group, the carbonyl radical of which is bonded to the oxygen atom and the acid radical of which is bonded to Y, and Y is a phosphorus-containing grouping which is chemically crosslinked to X via the phosphorus atom, and in which the phosphorus atom has the valency −3 to 5, in particular −2, −1, 0, +1, +2, +3, +4 or +5.

25. The method according to claim 24, wherein Y is selected from the group consisting of the following groupings ##STR00043## Z upon each occurrence, is the same or different and is selected from the group consisting of linear or branched and/or unsubstituted or substituted alkyl radicals, unsubstituted or substituted aryl radicals, unsubstituted or substituted heteroaryl radicals or acyl groups, the carbonyl radical of which is bonded to the phosphorus atom or A or B, the previously mentioned radicals being able to be substituted by at least one further structural element according to the above-illustrated formula I and/or by at least one further radical R.sup.1 and also from structural elements of the above-illustrated formula I and groupings —X—Y, A upon each occurrence, is the same or different and meaning oxygen or sulphur, B upon each occurrence, is the same or different and meaning nitrogen, and D upon each occurrence, is the same or different and being selected from the group consisting of linear or branched and/or unsubstituted or substituted alkyl radicals, unsubstituted or substituted aryl radicals, unsubstituted or substituted heteroaryl radicals, the previously mentioned radicals being able to be substituted optionally by at least one further structural element according to the above-illustrated formula I and/or by at least one further radical R.sup.1.

26. The method according to claim 23, wherein the phosphorus-containing organic oxyimide is halogen-free.

27. The method according to claim 23, wherein the phosphorus-containing organic oxyimide has the following structure:
E-R.sup.1 E is the radical set forth below, E being bonded to R.sup.1 via the oxygen atom, ##STR00044## R.sup.1 is defined as above and R.sup.1′ upon each occurrence, is the same or different and representing hydrogen, a linear or branched alkyl radical, a linear or branched alkylene radical, an aromatic radical, a heteroaromatic radical, or in the case of radicals R.sup.1 being bonded to form a ring, the ring being able to be saturated or unsaturated, substituted or unsubstituted and/or at least one or both radicals R.sup.1′, or the radicals R.sup.1′ bonded to form a ring, comprising at least one further structural element of the above-illustrated formula I.

28. The method according to claim 27, wherein the phosphorus-containing organic oxyimide has one of the subsequent formulae: ##STR00045## E and R.sup.1′ having the definition indicated above.

29. The method according to claim 23, wherein the phosphorus-containing organic oxyimide a) comprises a structural element of the general formula I and has one of the subsequent formulae ##STR00046## b) comprises two structural elements of the general formula I and has one of the subsequent formulae ##STR00047## n is 0, 1, 2, 3 or 4, and R.sup.2 is selected from the group consisting of optionally substituted alkylene-, cycloalkylene-, arylene-, heteroarylene- or bridging acyl radicals, or c) comprising three structural elements of the general formula I and having the subsequent formula ##STR00048##

30. The method according to claim 29, wherein R.sup.2 is selected from radicals of the group consisting of —(CH.sub.2).sub.n— with n=1 to 18, —CH(CH.sub.3)—, —C(CH.sub.3).sub.2—, —CH(CF.sub.3)—, —C(CF.sub.3).sub.2—, —O—, —S—, —SO.sub.2—, —NHCO—, —CO—, —OC(O)O— and the following groups ##STR00049## the cycloaliphatic or aromatic ring systems contained in the above groups being unsubstituted or substituted by one or more alkyl- and/or alkoxy groups, Q upon each occurrence, is the same or different and is selected from the group consisting of a chemical bond, —(CH.sub.2).sub.n— with n=1 to 18, —CH(CH.sub.3)—, —C(CH.sub.3).sub.2—, —CH(CF.sub.3)—, —C(CH.sub.3).sub.2—, —O—C(O)—O—, —O—, —S—, —SO.sub.2—, —NHCO—, and —CO—, and m is 0 or 1 to 3.

31. The method according to claim 23, wherein the phosphorus-containing organic oxyimide is selected from the group consisting of the following compounds ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054## y is 1 or 2 Alk is a linear or branched, substituted or unsubstituted alkyl radical, and Ar is a substituted or unsubstituted aryl radical or heteroaryl radical.

32. The method according to claim 23, wherein the structural element according to the general formula I is part of a polymer or copolymer, the polymers or copolymers having at least one of the following repeat units: ##STR00055##

33. The method according to claim 23, wherein the plastic materials are thermoplastic polymers, and selected from the group consisting of a) polymers made of olefins or diolefins, b) polystyrene, polymethylstyrene, polyvinylnaphthalene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene, styrene-isoprene, styrene-isoprene-styrene (SIS), styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile-acrylate (ASA), styrene-ethylene, styrene-maleic anhydride polymers including corresponding graft copolymers, graft copolymers made of methylmethacrylate, styrene-butadiene and ABS (MABS), c) halogen-containing polymers, d) polymers of unsaturated esters, polyacrylonitrile, polyacrylamides, copolymers, and polymethacrylimide, e) polymers made of unsaturated alcohols and derivatives, f) polyacetals, g) polyphenylene oxides and blends with polystyrene or polyamides, h) polymers of cyclic ethers, i) polyurethanes made of hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates, and polyureas, j) polyamides, blends of different polyamides, and blends of polyamides and polyolefins, k) polyimides, polyamideimides, polyetherimides, polyesterimides, poly(ether)ketones, polysulphones, polyethersulphones, polyarylsulphones, polyphenylene sulphide, polybenzimidazoles, and polyhydantoins, l) polyesters made of aliphatic or aromatic dicarboxylic acids and diols or made of hydroxycarboxylic acids, m) polycarbonates, polyester carbonates and also blends, n) cellulose derivatives, o) duromeric or elastomeric, non-thermoplastic plastic materials, and p) mixtures, combinations or blends of two or more of the previously mentioned polymers.

34. The method according to claim 23, wherein the at least one phosphorus-containing organic oxyimide is incorporated in combination with at least one further flame retardant, selected from the group consisting of a) inorganic flame retardants, b) nitrogen-containing flame retardants, c) radical formers, d) phosphorus-containing flame retardants, e) halogen-containing flame retardants based on chlorine and bromine, optionally in combination with Sb.sub.2O.sub.3 and/or Sb.sub.2O.sub.5, f) borates, optionally placed on silica as carrier material, g) sulphur-containing compounds, h) antidrip agents, i) silicon-containing compounds, j) carbon modifications, and combinations or mixtures hereof.

35. The method according to claim 23, wherein the radical formers are selected from the group consisting of a) N-alkoxyamines according to the subsequently illustrated structural formula, ##STR00056## wherein R.sup.3 is hydrogen or optionally substituted alkyl-, cycloalkyl-, aryl-, heteroaryl- or acyl radical, R.sup.4 is alkoxy-, aryloxy-, cycloalkoxy-, aralkoxy- or acyloxy radical, Z is hydrogen or optionally substituted alkyl-, cycloalkyl-, aryl-, heteroaryl- or acyl radical, the two radicals Z also being able to form a closed ring which can be substituted optionally by ester-, ether-, amine-, amide-, carboxy- or urethane groups, E is an alkoxy-, aryloxy-, cycloalkoxy-, aralkoxy- or acyloxy radical, b) azo compounds according to the subsequently illustrated structural formulae, ##STR00057## R.sup.5 is an alkyl-, cycloalkyl- or aryl radical, R.sup.6 upon each occurrence, is the same or different and meaning a linear or branched alkyl radical, R.sup.7 upon each occurrence, is the same or different and meaning hydrogen or a linear or branched alkyl radical, and R.sup.8 upon each occurrence, is the same or different and meaning an alkyl-, alkoxy-, aryloxy-, cycloalkyloxy-, aralkoxy- or acyloxy radical, c) dicumyl according to the formula ##STR00058## R.sup.7 having the previously indicated meaning, d) and/or polycumyl according to the formula ##STR00059## R.sup.7 is as defined above, and 2<n<100.

36. The method according to claim 34, wherein the phosphorus-containing organic oxyimide and the at least one further flame retardant are incorporated in a weight ratio of 99:1 to 1:99.

37. The method according to claim 36, wherein the phosphorus-containing organic oxyimide is selected from the group consisting of organic phosphites and phosphonites.

38. The method according to claim 23, wherein the phosphorus-containing organic oxyimide, relative to the plastic materials, is incorporated at 0.01 to 30% by weight.

39. The method according to claim 23, wherein at least one phosphorus-containing organic oxyimide is incorporated.

40. A flame-retardant and/or stabilised plastic material composition, comprising or consisting of: a) 60 to 99.9 parts by weight, of at least one plastic material, b) 0.1 to 40 parts by weight, of at least one phosphorus-containing organic oxyimide, containing at least one structural element of Formula I, ##STR00060## c) 0 to 25 parts by weight of at least one further flame retardant, and/or d) 0 to 25 parts by weight of at least one phosphorus-containing compound.

41. The flame-retardant and/or stabilised plastic material composition according to claim 40, which further includes: a) up to 40 parts by weight of at least one reinforcing- or filling material and/or b) up to 5 parts by weight of at least one additive from the class of phenolic antioxidants, phosphites, acid collectors, hindered amines, dispersants and combinations thereof.

42. The flame-retardant plastic material composition according to claim 40, wherein the additives are selected from the group consisting of UV absorbers, light stabilisers, stabilisers, hydroxylamines, benzofuranones, nucleation agents, impact strength enhancers, plasticisers, lubricants, rheology modifiers, processing aids, pigments, colourants, optical brighteners, antimicrobial active substances, antistatic agents, slip agents, antiblocking agents, coupling means, dispersants, compatibilisers, oxygen collectors, acid collectors, marking means or anti-fogging means.

43. A method for the production of a flame-retardant and/or stabilised plastic material composition according to claim 40, comprising incorporating a) 0.1 to 40 parts by weight of at least one phosphorus-containing organic oxyimide, comprising at least one structural element of Formula I, ##STR00061## and b) before, after or at the same time, 0 to 25 parts by weight, of at least one further flame retardant in 60 to 99.9 parts by weight, of at least one plastic material.

44. A moulded part, paint, or coating, produced from a flame-retardant plastic material composition according to claim 40.

Description

SYNTHESIS EXAMPLE 1

Synthesis of phosphoryl-tris-N-oxyphthalimide

[0192] There is added drop-wise to a dispersion of sodium N-oxyphthalimide (18.41 g; 9.9 mmol) in absolute THF (125 ml) under inert gas, phosphoryl chloride (3.0 ml; 3.3 mmol) and the mixture is subsequently agitated for two days, the result being decolouration of the dispersion. The insoluble components are separated by filtration and the mixture comprising the product is obtained without further cleaning after removal of the solvent on a rotary evaporator.

[0193] .sup.1H-NMR (500 MHz, DMSO): δ=7.82(S) ppm.

[0194] .sup.13C-NMR (126 MHz, DMSO): δ=164.05, 134.47, 128.73, 122.91, 39.52 ppm.

[0195] .sup.31P-NMR (202 MHz, DMSO): δ=0.31, −11.76 ppm.

SYNTHESIS EXAMPLE 2

Synthesis of phenoxyphosphoryl-bis-N-oxyphthalimide

[0196] There is added drop-wise to a dispersion of sodium N-oxyphthalimide (18.0 g; 9.7 mmol) in absolute THF (125 ml) under inert gas, phenyldichlorophosphate (7.1 ml; 4.7 mmol) and the mixture is subsequently agitated for two days, the result being decolouration of the dispersion. The insoluble components are separated by filtration and the mixture comprising the product is obtained without further cleaning after removal of the solvent on a rotary evaporator.

[0197] .sup.1H-NMR (300 MHz, DMSO); δ=7.82(S), 7.33-7.31(m)

[0198] .sup.31P-NMR (122 MHz, DMSO); δ=−6.58.

SYNTHESIS EXAMPLE 3

Synthesis of a 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene-N-hydroxyphthalimide adduct

[0199] There is added dropwise to a solution of N-hydroxyphthalimide (6.95 g; 42.6 mmol) and triethylamine (5.9 ml; 42 mmol) in absolute THF (100 ml), a solution of 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenathrene (10 g; 42.6 mmol) in absolute THF (50 ml) and the mixture is subsequently agitated for 12 hours at ambient temperature, the result being decolouration of the solution. After the end of the reaction, the product is filtered off, washed with water and subsequently obtained as a pure product by recrystallisation in toluene.

[0200] .sup.1H NMR (300 MHz, CDCl.sub.3): δ=8.27 (ddd, J=7.7, 1.5, 0.6 Hz, 1H), 8.05 (d, J=8.0 Hz, 1H), 7.99 (dd, J=8.0, 1.6 Hz, 1H), 7.86-7.80 (m, 2H), 7.80-7.77 (m, 1H), 7.77-7.71 (m, 2H), 7.59 (td, J=7.6, 1.0 Hz, 1H), 7.45, (ddd, J=8.5, 7.0, 1.6 Hz, 1H), 7.39-7.34 (m, 1H), 7.31 (ddd, J=8.0, 7.1, 1.6 Hz, 1H).

[0201] .sup.31P NMR (122 MHz, CDCl.sub.3): δ=2.58.

SYNTHESIS EXAMPLE 4

Synthesis of diphenoxyphosphoryl-N-oxyphthalimide

[0202] There is added drop-wise to a solution of N-hydroxyphthalimide (15.18 g; 93 mmol) and triethylene (13 ml; 93 mmol) in absolute DCM (400 ml), diphenoxyphosphoryl chloride (19.3 g; 93 mmol) and the mixture is subsequently agitated for 12 hours at ambient temperature, the result being decolouration of the solution. After the end of the reaction, the solution is washed three times with respectively 200 ml of water and subsequently with 200 ml of 10% NaHCO.sub.3 solution. After drying over calcium chloride and removal of the solvent, the product is obtained by recrystallisation in DCM/hexane 1:1.

[0203] .sup.1H-NMR (300 MHz, CDCl.sub.3): δ=7.93-7.85 (m, 2H), 7.85-7.76 (m, 2H), 7.48-7.36 (m, 8H), 7.36-7.20 (m, 2H).

[0204] .sup.31P-NMR (122 MHz, CDCl.sub.3): δ=−11.68 ppm.

B) Production and Testing of a Flame-Retardant Plastic Material Mixture According to the Invention

[0205] The extrusions of the polypropylene samples (DOW C766-03) are effected at a temperature of 190° C. and a screw speed of rotation of 150 rpm on an 11 mm twin-screw extruder (Process 11 of Thermo Scientific). The desired ratio of polymer and additives is firstly homogenised by mixing and supplied to the extrusion via volumetric metering.

[0206] Test pieces for the fire test are produced from the granulate at a temperature of 220° C. and a pressure of 2 t using a hydraulic 10 t press (Werner & Pfleiderer). For this purpose, the granulate is filled into the compression mould and this is transferred into the already preheated press. At a pressure of 0.5 t, the granulate is firstly melted for 60 s. After expiry of the melting time, the pressure is increased to 2 t and kept constant for a further 3 min. Whilst maintaining the contact pressure, the mould is cooled to 60° C. and thereafter the test pieces are removed. The test pieces have the following dimensions according to the standard: 127.5×12.5×1.5.

[0207] The examples and comparative examples according to the invention contained in Table 1 were tested according to DIN EN 60695-11-10 and the burning times and classification according to the standard were obtained:

TABLE-US-00001 TABLE 1 Compositions in polypropylene and results of the fire test Burning times Total of the secondary burning times of 5 test Classification Composition pieces with 2 according to Flame flame impingements DIN EN Example retardant [in seconds] 60695-11-10 Comparative 15% aluminium >200 not classified example 1 diethyl- (state of phosphinate the art) Comparative 20% aluminium 170 not classified example 2 diethyl- phosphinate Example 1 15% aluminium 21.8 V-2 according diethyl- to the phosphinate invention 2% phosphoryl- tris-N-oxy- phthalimide (synthesis example 1) Example 2 15% aluminium 47.2 V-2 according diethyl- to the phosphinate 2% invention phenoxyphosphoryl- bis-N-oxy- phthalimide (synthesis example 2) Example 3 6% aluminium 16.5 V-2 according diethyl- to the phosphinate 4% invention phenoxyphosphoryl- bis-N-oxy- phthalimide (synthesis example 2) Example 4 15% diethyl- 83.8 V-2 according aluminium to the phosphinate 2% invention 10-choro-9,10- dihydro-9-oxa- 10-phosphaphen- anthrene N- hydroxyphthal- imide adduct (synthesis example 3) Example 5 15% diethyl- 23.9 V-2 according aluminium to the phosphinate invention 2% diphenoxy- phosphoryl-N- oxyphthalimide (synthesis example 4) Example 6 10% diethyl- 19.9 V-2 according aluminium to the phosphinate invention 5% diphenoxy- phosphoryl-N- oxyphthalimide (synthesis example 4) Aluminium diethylphosphinate (Exolit OP 1230, manufacturer: Clariant SE)

[0208] The examples according to the invention are self-extinguishing after removal of the source of ignition and have surprisingly reduced burning times relative to the comparative example, a classification according to V-2 is obtained