USE OF ORGANIC OXYIMIDE SALTS AS FLAME RETARDANTS, FLAME-RETARDANT PLASTIC COMPOSITIONS, METHOD FOR THE PRODUCTION THEREOF AND MOULDED PART, PAINT OR COATING

Abstract

The invention relates to the use of organic oxyimide salts as flame retardants for plastics and to a corresponding flame retardant plastic composition. The invention also relates to a method for producing said type of plastic composition or a moulded part produced therefrom, a moulding compound, a moulded part, paint or a coating.

Claims

1-17. (canceled)

18. A method for imparting flame retardancy to a plastic material comprising incorporating an organic oxyimide salt having at least one structural element of formula I ##STR00031## wherein R.sup.1 is selected from the group consisting of inorganic cations, organic cations, and combinations thereof, into the plastic material.

19. The method according to claim 18, wherein the inorganic cations are selected from the group consisting of metal cations, and/or the organic cations are selected from the group consisting of nitrogen and/or phosphorus-containing organic cations.

20. The method according to claim 18, wherein the organic oxyimide salt is halogen-free.

21. The method according to claim 18, wherein the organic oxyimide salt has the structure ##STR00032## wherein R.sup.1 is selected from the group consisting of inorganic cations, organic cations, and combinations thereof, and R.sup.1′, upon each occurrence, is the same or different and is a linear or branched alkyl radical, a linear or branched alkylene radical, an aromatic radical, a heteroaromatic radical or both radicals R.sup.1′ are joined to form a ring, the ring being saturated or unsaturated, substituted or unsubstituted and/or at least one or both radicals R.sup.1′ or the radicals R.sup.1′ are joined to form a ring comprising at least one further structural element of formula I.

22. The method according to claim 18, wherein the organic oxyimide salt a) comprises a structural element of formula I and has a structure according to one of the formulae: ##STR00033## ##STR00034## b) comprises a structural element of formula I and has a structure according to one of the subsequent formulae: ##STR00035## wherein 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) comprises three structural elements of formula I and has a structure according to the formula ##STR00036##

23. The method according to claim 22, wherein R.sup.2 is selected from 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)—, —O—, —S—, —SO.sub.2—, —NHCO—, —CO—, and —OC(O)O— and groups ##STR00037## wherein the cycloaliphatic or aromatic ring systems contained in the above groups are 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(CF.sub.3).sub.2, —O—, —S—, —SO.sub.2—, —NHCO—, —CO—, and —C(O)—O—, and m is 0 or 1 to 3.

24. The method according to claim 18, wherein the plastic materials are thermoplastic polymers and are 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 and graft copolymers made of methylmethacrylate, styrene-butadiene and ABS (MABS), c) halogen-containing polymers, d) polymers of unsaturated esters, e) polymers made of unsaturated alcohols and derivatives thereof, 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, j) polyamides, k) polyimides, polyamideimides, polyetherimides, polyesterimides, poly(ether)ketones, polysulfones, polyethersulfones, polyarylsulfones, polyphenylenesulfides, polybenzimidazoles, or polyhydantoins, l) polyesters made of aliphatic or aromatic dicarboxylic acids and diols or made of hydroxycarboxylic acids, m) polycarbonates, polyestercarbonates and blends thereof, n) cellulose derivatives, o) elastomeric, non-thermoplastic or duroplastic plastic materials, and p) mixtures, combinations, or blends thereof.

25. The method according to claim 18, which includes incorporating 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, g) sulfur-containing compounds, h) antidrip agents, i) silicon-containing compounds, and j) combinations or mixtures thereof.

26. The method according to the claim 25, wherein the radical formers are selected from the group consisting of a) N-alkoxyamines according to the structural formula, ##STR00038## wherein R.sup.3 is hydrogen or an optionally substituted alkyl-, cycloalkyl-, aryl-, heteroaryl- or acyl-radical, R.sup.4 is an alkoxy-, aryloxy-, cycloalkoxy-, aralkoxy- or acyloxy-radical, and Z is hydrogen or an optionally substituted alkyl-, cycloalkyl-, aryl-, heteroaryl- or acyl-radical, the two radicals Z also being able to form a closed ring which is substituted optionally by ester-, ether-, amine-, amide-, carboxy- or urethane-groups, b) azo compounds according to the structural formula, ##STR00039## wherein R.sup.5 is an alkyl-, cycloalkyl- or aryl-radical, R.sup.6 upon each occurrence, is the same or different and is a linear or branched alkyl-radical, R.sup.7 upon each occurrence, is the same or different and is hydrogen or a linear or branched alkyl-radical, and R.sup.8 upon each occurrence, is the same or different and is an alkyl-, alkoxy-, aryloxy-, cycloalkyloxy-, aralkoxy- or acyloxy-radical, c) dicumyl compounds according to the structural formula ##STR00040## wherein R.sup.7 upon each occurrence, is the same or different and is hydrogen or a linear or branched alkyl-radical, d) and/or a polycumyl compound according to the structural formula ##STR00041## wherein R.sup.7 upon each occurrence, is the same or different and is hydrogen or a linear or branched alkyl-radical, and 2<n<100.

27. The method according to claim 25, wherein the organic oxyimide salts and the at least one further flame retardant are incorporated in a weight ratio of 99:1 to 1:99.

28. The method according to claim 18, wherein the organic oxyimide salts are incorporated in combination with at least one phosphorus-containing compound.

29. The method according to claim 18, wherein the organic oxyimide salts, relative to the plastic materials, are incorporated at 0.01 to 30% by weight.

30. A flame-retardant 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 organic oxyimide salt, comprising at least one structural element of the formula I, ##STR00042## R.sup.1 being selected from the group consisting of inorganic and organic cations, c) 0 to 25 parts by weight of at least one further flame retardant, and d) 0 to 25 parts by weight, of at least one further phosphorus-containing compound.

31. The flame-retardant plastic material composition according to claim 30, 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 selected from the class of phenolic antioxidants, phosphites, acid collectors, hindered amines, dispersants, and combinations thereof.

32. The flame-retardant plastic material composition according to claim 30, which includes one or more additives 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 and anti-fogging means.

33. A method for the production of a flame-retardant plastic material composition, comprising introducing into the plastic material a) 0.1 to 40 parts by weight of at least one organic oxyimide salt, comprising at least one structural element of the subsequently illustrated formula I, ##STR00043## R.sup.1 being selected from the group consisting of inorganic cations, organic cations, and combinations thereof, b) before, after or at the same time, introducting 0 to 25 parts by weight, of at least one further flame retardant and/or c) before, after or at the same, introducing 0 to 25 parts by weight, of at least one phosphorus-containing compound, in 60 to 99.9 parts by weight, of at least one plastic material.

34. A moulded part, paint, or coating comprising a flame-retardant plastic material composition according to claim 30.

35. The moulded part, paint, or coating according to claim 34, which is an injection moulded part, foil, coating, foam, fibre, cable or pipe, which is produced by an extrusion, injection moulding, blow-moulding, or pressing process.

Description

SYNTHESIS EXAMPLES

Example 1

Synthesis of Sodium N-oxyphthalimide

[0190] Analogously to the literature (monthly journals for chemistry 137, 1591-1595 (2006)) there is added to a solution of N-hydroxyphthalimide (61.7 g; 378 mmol) in absolute ethanol (800 ml) with agitation, an equivalent quantity of sodium hydroxide (15.1 g; 378 mmol) which is subsequently heated for two hours with reflux. After cooling the solution, the formed product is filtered and washed with absolute ethanol. The product is obtained quantitatively as a red solid after drying in the vacuum oven at 100° C. for 12 hours.

[0191] .sup.1H-NMR (500 MHz, D20); δ=7.49 (dd, J=5.3, 3.0 Hz, 1H), 7.35 (dd, J=5.3, 3.0 Hz, 1H) ppm.

[0192] .sup.13C-NMR (126 MHz, D20); δ=169.11, 133.29, 129.08, 121.44 ppm.

Example 2

Synthesis of an N-oxyphthalimide Zinc Salt

[0193] To a solution of sodium N-oxyphthalimide (5.97 g; 32.2 mmol) in H.sub.2O (400 ml), zinc nitrate hexahydrate (4.8 g; 16.1 mmol) is added with agitation. After approx. half an hour, an orange-coloured precipitate is formed, whereupon the dispersion is stored for a further 12 hours at room temperature. The product is subsequently filtered off via a Büchner funnel, washed with H.sub.2O (100 ml) and dried at 140° C. for 12 hours under vacuum.

[0194] .sup.1H-NMR (300 MHz, DMSO-d.sub.6); δ=7.74-7.40 (m, 1H).

Example 3

Synthesis of an N-oxyphthalimide Melaminium Salt

[0195] To a solution of melamine (10 g; 79.3 mmol) in hot H.sub.2O (200 ml), N-hydroxyphthalimide (12.93; 79.3 mmol) is added and the mixture thereupon heated for 3 hours with reflux. Subsequently, the mixture is stored for a further 12 hours at room temperature. The orange-coloured product is thereupon filtered off via a Büchner funnel, washed with H.sub.2O (100 ml) and dried for 12 hours at 140° C. under vacuum.

[0196] .sup.1H-NMR (300 MHz, DMSO-d6); δ=7.82 (s, 1H), 6.23 (s, 1H).

Example 4

Synthesis of an N-oxyphthalimide Polyvinyl Diaminotriazine Salt

[0197] To a dispersion of poly-2-vinyl-4,6-diamino-1,3,5-triazine (5 g; 36.5 mmol) in hot H.sub.2O (50 ml), N-hydroxyphthalimide (5.95 g; 36.5 mmol) is added with agitation and the dispersion heated for 3 hours with reflux. Subsequently, the mixture is stored for a further 12 hours at room temperature. The yellowish and insoluble product is thereupon filtered off via a Büchner funnel and subsequently dried at 140° C. for 12 hours under vacuum.

[0198] Production and Testing of a Flame-Retardant Plastic Material Mixture According to the Invention

[0199] 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.

[0200] 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.

[0201] 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% diethyl- >200 Not classified example 1 aluminium (state of phosphinate the art) Comparative 20% diethyl- 170 not classified example 2 aluminium phosphinate Example 3 15% diethyl- 30.9 V-2 according to aluminium the invention phosphinate 2% sodium N- oxyphthalimide (example 1) Example 4 8% phosphonate + 54.4 V-2 according to 2% sodium N- the invention oxyphthalimide (example 1) Example 5 15% diethyl- 27.2 V-2 according to aluminium the invention phosphinate 2% zinc salt (example 2) Example 6 15% diethyl- 27 V-2 according to aluminium the invention phosphinate 2% melaminium salt (example 3) Example 7 10% phosphazene 4.2 V-2 according to 5% melaminium the invention salt (example 3) Example 8 15% diethyl- 33.3 V-2 according to aluminium the invention phosphinate 2% polyvinyl diaminotriazine salt (example 4)

[0202] Phosphazenes (SBP-100, Otsuka Chemical Co., Ltd.)

[0203] Aluminium diethylphosphinate (Exolit OP 1230, Clariant SE)

[0204] Phosphonate (Aflammit PCO 900, Thor GmbH)

[0205] 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.