WO2014173908A1 - Improved composition and use thereof as a flameproofing agent - Google Patents

Abstract

The invention relates to a composition, which has improved properties in particular as a flameproofing agent, and use of the composition as a flameproofing agent in particular for plastics, for example in form of injection-molded parts, films, coatings, foams, fibers, cables, and pipes.

Description

 Improved composition and its use as a flame retardant

description

The present invention relates to a composition which is particularly suitable as a flame retardant.

Most plastics are flammable and relatively flammable. In order to reduce or eliminate the risk of fire of plastics in certain applications, it is therefore imperative to reduce the flammability and to use flame-retardant plastic compositions. For this purpose, flame retardants are usually added to the plastic with the aim of preventing the ignition for a certain time or to significantly delay the spread of fire. Traditional flame retardants are based on chlorine- and bromine-containing compounds (in conjunction with antimony trioxide), on phosphorus-containing and nitrogen-containing compounds and on inorganic hydroxides. In recent times, halogen-free flame retardant solutions are preferred for environmental reasons. For the production of flame-retardant plastics, there are a variety of flame retardants, which are usually used substrate-specific for a particular polymer and a specific application according to the underlying standards.

Particularly pronounced is the problem of flammability in plastics z. B. from the group of polyolefins, such as. As polypropylene or polyethylene, polystyrenes and polyurethanes. These have been particularly sensitive proved to be flammable. In particular, for applications in the field of household electronics, in the transport sector (cars, trains, aircraft, ships) or for building materials and furniture so there is a strong demand

Flame retardants that can inhibit the high flammability of these plastics. For example, for effective flame retardancy of

polyolefinic plastics and of polyurethanes in particular inorganic flame retardants proposed, such as magnesium dihydroxide (MDH) or

Aluminum trihydroxide (ATH). However, a major disadvantage of these inorganic additives is that they must be added in very high amounts, often over 60 wt .-%, in order to achieve the necessary flame retardant effect.

From DE 10 2004 047 257 a compound class of flame retardants is known which relates to asymmetrical and symmetrical phosphorus-containing heptazine derivatives and oligomers and polymers derived therefrom. The in the

DE 10 2004 047 257 described phosphorus-containing heptazine derivatives are suitable as flame retardants for plastics, textiles, wood products, paper, cardboard, plasters, insulation materials, building material composites and polymeric foams.

Despite the good results, with the flame retardants according to

DE 10 2004 047 257, it has been found that another

Increasing the flame retardancy would be desirable. This is especially true when using the flame retardant according to DE 10 2004 047 257 in certain plastics, such as. As polyolefins, in which a further increase in the flame retardant effect appears desirable for technical and economic reasons.

It is an object of the present invention to provide further improved flame retardants having an improved property profile, i. With

improved flame retardant effect.

The stated object is achieved by a composition comprising

(a) unsymmetrical and symmetrical phosphorus-containing heptazine derivatives represented by the formula (1), unsymmetrical and symmetrical phosphorus-containing melamine derivatives represented by the formula (Ia)), unsymmetrical and symmetric ones phosphorus-containing melam derivatives (1,3,5-triazines-2,4,6-triamines-n - (4,6-diamino-l, 3,5-triazine-2-yl) represented by the formula (lb)) , and / or unsymmetrical and symmetrical phosphorus-containing melon derivatives (poly [8-amino-1,3,4,6,7,9,9b-heptaazaphenalene-2,5-diyl) imino] represented by the formula (Ic))

(Formula 1))

(Formula (2))

(Formula (3)) and / or

 (Formula (4)) wherein, in the formula (1c), n = 2 to 100 (or> 2),

where R _a , R _b , R _c and R _{d are} independently an azide group - N ₃ or a -N = PR _! R ₂ R ₃ group, with the proviso that at least one radical of R _a , R _b and R _{c is} a -N = PRiR ₂ R ₃ group, wherein Ri, R ₂ , and R _{3 are} independently a radical, selected from the group a consisting of a straight or branched (Ci-Ci ₂₎ -alkyl, (C ₃ -C ₇₎ cycloalkyl radical, a straight or branched chain (Ci-Ci ₂₎ alkenyl radical, a straight or branched (Ci-Ci ₂₎ alkoxy radical, furyl, furanyl, benzofuranyl, thienyl, thiazolyl, benzothiazolyl, thiadiazolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyrazinyl, benzothienyl, morpholinyl, thiomorpholinyl, piperidinyl, piperazinyl, pyrrolidinyl, Pyrimidinyl, imidazolinyl, pyrazolidinyl, phenyl,

Phenoxy, benzyl, benzyloxy, naphthyl, naphthoxy, di (C ₁ -C ₆ ) alkylamino, tri (C ₁ -C ₆ ) alkylsilyl or pyridyl each having one to five substituents independently selected from the group consisting of β a straight-chain or branched (Ci- C ₆₎ alkyl radical, a (C ₃ -C ₇₎ cycloalkyl radical, a straight or branched chain (Ci-C ₆₎ alkenyl group, a straight or branched chain (Ci-C ₆₎ alkoxy, Halogen, hydroxy, amino, di (C ₁ -C ₆ ) alkylamino, nitro, cyano, benzyl, 4-methoxybenzyl, 4-nitrobenzyl, phenyl, and 4-methoxyphenyl, and oligomers and polymers derived therefrom; at least one compound from the group of

Radical generators. It has surprisingly been found that the combination of a phosphorus-containing heptazine derivative (a) with at least one compound (b) from the group of radical generators leads to a synergistic effect of the flameproofing effect.

In particular, it has surprisingly been found that the addition of compounds from the group of radical generators makes it possible to achieve a greater reduction of the afterburn times with a reduced amount of total additive. This is particularly surprising, since the use of radical generators alone does not achieve any or only a low flame retardancy. By the

inventive combination of such radical generators with

By contrast, unsymmetrical and symmetrical phosphorus-containing heptazine derivatives of the formula (1), (2), (3) and (4) make it possible to use the

To reduce total amount of flame retardant and at the same time one

To improve the flame retardancy. This is shown in detail in the examples (see Table 1).

There is thus a most surprising synergistic effect of

Single components of the compositions according to the invention, since it allows the addition of radical generators to achieve an improved flame retardancy with reduced material costs.

In a preferred embodiment of the present invention, the compounds (a) used are symmetrical phosphorus-containing heptazine derivatives represented by the formula (Ib),

(Formula (Ib)) wherein R _1; R ₂ , and R ₃ independently represent a radical selected from the group a, consisting of a straight-chain or branched-chain (Ci-Ci ₂ ) -alkyl radical, a (C ₃ -C ₇ ) -cycloalkyl radical, a straight-chain or branched-chain (Ci -C ₂₎ alkenyl, a straight or branched (Ci-Ci ₂₎ alkoxy, furyl, furanyl, benzofuranyl, thienyl, thiazolyl, benzothiazolyl, thiadiazolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyrazinyl, benzothienyl, morpholinyl, thiomorpholinyl, Piperidinyl, piperazinyl, pyrrolidinyl, pyrimidinyl, imidazolinyl, pyrazolidinyl, phenyl, phenoxy, benzyl, benzyloxy, naphthyl, naphthoxy, di (C ₁ -C ₆ ) alkylamino, tri (C ₁ -C ₆ ) alkylsilyl or pyridyl, each containing one to five Substituents independently selected from the group ß, consisting of a straight-chain or branched-chain (Ci-C ₆ ) - alkyl, a (C ₃ -C ₇ ) -cycloalkyl, a straight-chain or branched-chain (Ci-C ₆ ) -Alkenylrest, a m straight-chain or branched-chain (Ci-C ₆ ) - alkoxy, halogen, hydroxy, amino, di (Ci-C ₆ ) alkylamino, nitro, cyano, benzyl, 4-methoxybenzyl, 4-nitrobenzyl, phenyl, and 4-methoxyphenyl substituted and oligomers and polymers derived therefrom.

Preferably, the group β comprises the above substituents in a form which have no halogen-containing groups. The group β is therefore preferably in non-halogenated form.

The phosphorus-containing heptazine derivatives (a) used according to the invention are usually air-stable and colorless / white.

In a particularly preferred embodiment of the present invention, R _1; R ₂ , and R _{3 of} the phosphorus-containing heptazine derivative (a) according to the above formula (lb) are each an aromatic radical which is above

Oxygen is bound, esp. -O-phenyl (phenoxy) or in each case m-kresyloxy, -1-naphthyloxy or 2-naphthyloxy or 2-biphenyloxy or 4-biphenyloxy.

In comparison to the conventional flame retardants of the prior art, the phosphorus-containing heptazine derivatives (a) which can also be referred to as melem phosphoranylides according to the invention can be the melamine, melamine or melon derivatives, by appropriate selection of the radicals with regard to the physical and chemical properties of the resulting links This class of substances can be advantageously varied and thus tailored in a simple manner specifically for a particular application.

With regard to the use of the inventively used phosphorus-containing heptazine derivatives (a), the phosphorus melamine, melamine and melon derivatives as part of a flame retardant composition so for example advantageous increased solubility of the derivative in a plastic to be protected as well as better adaptation the

Application requirements are achieved. The substance class of the phosphorus-containing heptazine, melamine, melam and melone derivatives used according to the invention offers a better one, simply because of their chemical structure

Compatibility and incorporation by e.g. Meltability or solubility in plastics as melon and meiern, which are used as solids.

Furthermore, the phosphorus-containing compounds used according to the invention

Heptazine, melamine, melamine and melone derivatives have the advantage that they can be designed halogen-free with respect to a flame retardant with respect to the radicals Ri, R ₂ and R ₃ and thus in comparison to the halogen-containing

Flame retardants of the prior art are environmentally friendly.

According to a further embodiment of the present invention, the phosphorus-containing heptazine, melamine, melam and melone derivatives may also be in the form of oligomer or polymer, with the latter containing, for example, structural units which contain two or more bridging phosphine groups or

Phosphazene linkages are exemplified as shown in formula (2b) below for heptazine derivatives:

(Formula (2b)) Preferred bridges for R ₂ are -O-phenyl-1,3-O-, -O-phenyl-1,4-O- and -O-naphthyl-O-. It is possible that the polymers are also present in crosslinking form.

Radical generators are in the context of the present invention, compounds which can generate by thermal and radiation-induced cleavage esp. By light radicals. A comprehensive presentation of such radical generators (also called free radical generator or radical initiators) can be found, for. See, for example, E.T. Denisov, T.G. Denisova, T.S. Pokidova, Handbook of free radical initiators, Wiley 2003. However, many free radical generators, such as peroxides or hydroperoxides, are used in the polymerization of monomers and in the synthesis of plastics and are required for these applications

Decomposition temperatures below 100 ° C. However, suitable free radical generators for the applications herein are those which have sufficient thermal stability for the plastics or coating processing processes, i. form during processing no or only very small amounts of radicals and only at higher temperatures, as they occur only in case of fire, spontaneously generate radicals. The respective processing processes and temperatures for coatings and plastic processing processes are known to the person skilled in the art. Plastic processing and related

Temperatures can also be taken from the specialist literature such. B. Domininghaus, P. Eisner, P. Eyerer. T. Hirth, Kunststoffe, 8th edition, Springer 2012.

In a preferred embodiment, the inventive

Composition is such that the at least one compound from the group of radical generators comprises one or more compounds having at least one functional group selected from compounds with

 -N = N- (azo group)

-NH-HN- (hydrazine)

> C = N-NH- (hydrazone)

> C = N-N = C <(azine)

-N = N-N <(triazene)

-S-S- (disulfide, polysulfide)

-S-H (thiol)

As well as connections based on thiuram

dithiocarbamates

Mercaptobenzothiazoles and / or

Sulfenamides.

In an alternative preferred embodiment, the composition according to the invention is designed such that it comprises at least one compound from the group of radical generators, with the proviso that it is not a compound having a NOR (alkoxyamine) group.

For the processing of plastics in the melt, it is advantageous for the radical generators used to have a thermal stability of at least 150 ° C., preferably of at least 180 ° C., very preferably of at least 200 ° C. The thermal stability of a compound can be z. B. by thermogravimetric analysis (TGA) are determined, wherein the weight loss is measured by decomposition at a certain temperature. Sufficient thermal stability is determined if at the measurement temperature no or only a low percentage decomposition tolerable for the incorporation process is detected. Suitable free radical generators therefore preferably consist of molecules with the structural elements

-N = N- (azo group)

-NH-HN- (hydrazine)

> C = N-NH- (hydrazone)

> C = N-N = C <(azine)

-N = N-N <(triazene)

-S-S- (disulfide, polysulfide)

-S-H (thiol).

Other suitable sulfur compounds are also Thiuramsulfide such. Tetramethylthiuram disulfide, dithiocarbamates, e.g. Zinkdiethyldithiocarbamat or Natriumdimethyldithiocarbamat, mercaptobenzothiazoles such. B. 2-mercaptobenzothiazole and sulfenamides such. N, N-dicyclohexyl-2-benzothiazolesulfenamide.

Example of a polysulfide is elemental sulfur, other polysulfides are described for example in US 4218332. The preparation of suitable azo compounds is for example in M. Aubert et. al. Macromol. Be. Eng. 2007, 292, 707-714 or in WO 2008101845, the preparation of hydrazones and azines in M. Aubert et al., Pol. Adv. Technol. 2011, 22, 1529-1538, the preparation of triazenes in W. Pawelec et al., Pol. Degr. Rod. 2012, 97, 948-954. Disulfides, polysulfides, thiols, thiuram sulfides, dithiocarbamates, mercaptobenzothiazoles and sulfenamides are commercially available.

Disulfides and polysulfides are preferred among the described structural elements, a particularly preferred compound being distearyl disulfide, which is commercially available under the tradename Hostanox (RTM) from Clariant SE.

It has proven to be particularly preferable if radical generators from the group of C-C radical generators are selected. For the purposes of the present invention, C-C radical generators are compounds which can generate tertiary carbon radicals by thermal or radiation-induced cleavage, in particular by light. Such C-C radical generators are described, for example, in E.T. Denisov, T.G.

Denisova, T.S. Pokidova, Handbook of Free Radical Initiators, Wiley 2003.

Particularly good results are achieved when radical generators,

be used in particular in the form of C-C radical generators that decompose thermally induced above 180 ° C.

Particularly good results are achieved when radical generators are used, the

Dicumyl (CAS No. 1889-67-4, Formula 5)

and or

und/oder Polycumyl-1,4 (CAS No. 25822-43-9, Formula 6)

and or

Polycumyl-1,3 (CAS No. 25822-44-0).

In a particularly preferred embodiment, for the polycumyl-1,4 and / or the polycumyl-1,3 n in the range of 2 to 1,000, particularly preferably in the range of 2 to 20.

Polycumyl can be prepared by polyrecombination of 1,4-diisopropylbenzene or 1,3-diisopropylbenzene by reaction with inorganic or organic peroxides as described e.g. By V.V. Korshak in Polymer Science USSR, 1 (1960), 341-350 and in Polymer Science USSR, 3 (1962), 925-935. This gives high molecular weight products

(Molecular weight 10000-50000). Another possibility for the preparation of polycumyl-1,4 is shown in DE 4437466. Here, the synthesis is carried out by reaction of 1,4-diisopropylbenzene with di-tert-butyl peroxide with an excess of 1,4-diisopropylbenzene. According to this process, colorless oligomeric products having an average molecular weight of 1000 (degree of polymerization about 3-7) are obtained.

In a particularly preferred embodiment, the composition according to the invention is such that compound (b) is selected from the group of radical generators dicumyl (CAS No. 1889-67-4, formula 5).

In an alternative preferred embodiment, the composition of the invention is such that compound (b) is selected from the group of radical generators polycumyl-1,4 (CAS No. 25822-43-9, formula 6). In a particularly preferred embodiment, the polycumyl-1,4 is present such that n is in the range from 2 to 1000, more preferably in the range from 2 to 20. Furthermore, mixtures of different radical generators can be used, for. B. radical generators, a different

Have decomposition temperature. Dicumyl and polycumyl are commercial products, the z. B. from United Initiators GmbH & Co KG, Pullach, Germany are available.

The present invention also relates to the use of a composition as described above as a flame retardant, in particular for plastics and coatings.

Suitable plastics are: a) polymers of olefins or diolefins such. As polyethylene (LDPE, LLDPE, VLDPE, MDPE, HDPE), metallocene PE (m-PE), polypropylene, polyisobutylene, poly-4-methyl-pentene-l, polybutadiene, polyisoprene, polycyclooctene, and copolymers in the form of statistical Gradient or block structures such. Polypropylene-polyethylene (EP), EPM or EPDM, ethylene-vinyl acetate (EVA), ethylene-acrylic ester; b) polystyrene, polymethylstyrene, styrene-butadiene, styrene-butadiene-styrene (SBS), styrene-isoprene, styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile-acrylate (ASA) styrene-maleic anhydride polymers including corresponding graft copolymers such as z. Styrene on butadiene or maleic anhydride on SBS; c) halogen-containing polymers such. B. polyvinyl chloride and

 polyvinylidene chloride; d) polymers of unsaturated esters such. For example, polyacrylates and

 Polymethacrylates such as PMMA, polyacrylonitrile; e) polymers of unsaturated alcohols and derivatives, e.g.

Polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral; f) polyacetals, such as. For example, polyoxymethylene; g) polyphenylene oxides and blends with polystyrene; h) polyurethanes, in particular linear polyurethanes; i) polyamides such as. As polyamide-6, 6.6., 6.10. 4.6, 6.12, 12.12., Polyamide 11, polyamide 12 and (partially) aromatic polyamides such. For example, polyphthalamides; j) polyimides, polyamideimides, polyetherimides, polyketones, polysulfones,

 Polyethersulfones, polyphenylene sulfide; k) polyesters such. For example, polyethylene terephthalate and polybutylene terephthalate, polylactic acid;

I) polycarbonate; m) cellulose derivatives such. B. cellulose nitrate, cellulose acetate,

 cellulose propionate; n) and mixtures, combinations or blends of two or more of the aforementioned polymers.

In a particularly preferred embodiment, the compositions according to the invention are used as flame retardants for plastics from the group of polyolefins, polystyrenes and polyurethanes. Very particular preference is given to polyolefins such as polyethylene, polypropylene or diene elastomers, copolymers of these polymers and their blends with other polymers.

Preferably, the plastic contains 5-30% of the flame retardant combination.

Optionally, the plastic except the inventive

Flame retardants nor flame retardants and / or additives are added. Suitable further additives are, for example, from the group of UV absorbers, light stabilizers, stabilizers, the

Hydroxylamines, the benzofuranones, the metal deactivators, the

Filler deactivators, nucleating agents, toughening agents, plasticizers, lubricants, rheology modifiers, processing aids, pigments, dyes, optical brighteners, antimicrobials, antistatics, slip agents, antiblocking agents, coupling agents, dispersants, compatibilizers, oxygen scavengers, acid scavengers, marking agents and / or antifogging agents. a) Suitable further flame retardants are, for. B. a) inorganic

Flame retardants such. B. Al (OH) ₃ , Mg (OH) ₂ , AIO (OH), phyllosilicates such as As montmorillonite, and / or organically modified, double salts, such as. As Mg-Al silicates MgC0 ₃ , huntite, hydromagnesite or halloysite and Sb ₂ 0 ₃ , Sb ₂ 0 ₅ , M0O3, zinc stannate, zinc hydroxystannate, b) nitrogen-containing flame retardants such. As melamine, Meiern, melam, melon, melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, allantoin, Phosphacene esp. Melamine cyanurate, melamine phosphate,

 Melamine pyrophosphate, dimelamine phosphate, melamine polyphosphate, ammonium polyphosphate, melamine borate, melamine hydrobromide

c) Phosphorus-containing flame retardants, e.g. red phosphorus, phosphates such. As resorcinol diphosphate, bisphenol A diphosphate and their oligomers, triphenyl phosphate, phosphinates such. For example, salts of hypophosphorous acid and its derivatives such as

 Diethylaluminum phosphinate or aluminum phosphinate,

 Aluminum phosphonate, aluminum phosphite, phosphonate esters, oligomeric and polymeric derivatives of methane phosphonic acid, 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO) and substituted compounds d) chlorine and bromine containing compounds such as e.g. B. polybrominated

 Diphenyloxides, tris (3-bromo-2,2-bis (bromomethyl) propyl phosphate, ethylene bis (tetrabromophthalimide), tetrabromo-bisphenol A, brominated polystyrene, brominated polybutadiene, brominated epoxy resin,

Polypentabrombenzylacrylat, optionally in combination with Sb ₂ 0 ₃ and / or Sb ₂ 0 ₅ , e) borates such as zinc borate or calcium borate f) antidrip agents such. B. polytetrafluoroethylene

Be further to the flame retardants of the invention

Flame retardants used, the plastic preferably contains 5-30% total of flame retardants. In a preferred embodiment, the compositions contain in particular acid scavengers, for. B. based on salts of long-chain acids such. B.

Calcium stearate, magnesium stearate, zinc stearate, calcium lactate or of

Hydrotalcites and / or stabilizers from the group of phenolic

Antioxidants, the phosphites / phosphonites and / or light stabilizers from the group of hindered amines (HALS) and / or dispersants.

Suitable light stabilizers, for example compounds on the basis of 2- (2 ^{'hydroxyphenyl)} benzotriazoles are, 2-hydroxybenzophenones, esters of benzoic acids, acrylates, oxamides, and 2- (2-hydroxyphenyl) -l, 3,5-triazines.

Suitable phenolic antioxidants are, for example, alkylated monophenols, alkylated hydroquinones, tocopherols, alkylidenebisphenols,

Hydroxybenzylverbindungen, Benzylphosphonate and esp. Esters and amides of ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols

such as Octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate,

Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, 1,3,5-trimethyl-2 , 4,6-tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4 - hydroxybenzyl) benzene, triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, N, N ^, -hexane-1,6-diyl-bis [3- (3,5-) di-tert-butyl-4-hydroxyphenyl) propionic acid amide.

Suitable phosphites / phosphonites are, for example:

Triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites,

Tri (nonylphenyl) phosphite, trilauryl phosphites, trioctadecyl phosphite,

Distearyl pentaerythritol diphosphite, tris- (2,4-di-tert-butylphenyl) phosphite,

Diisodecylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis ( 2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4 ^, -biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo [d, g] -l, 3,2-dioxaphosphocine, bis (2,4-di-tert-butyl -6- methylphenyl) methyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -l, 3,2-dioxaphosphocin, ^2,2, 2 "-nitrilo [triethyltris (3,3 ', ^5,5, -tetra-- ^■ eΓt-butyl-l, ^{-biphenyl-2,2,} - diyl) phosphite], 2-ethylhexyl (3,3 ^ ^5,5, -tetra-- ^■ eΓt-butyl-l, ^{-biphenyl-2,2,} - diyl)) phosphite, 5-butyl-5-ethyl-2- ( 2,4,6-tri-tert-butylphenoxy) -l, 3,2-dioxaphosphirane.

Other suitable stabilizers are aminic antioxidants and

Hydroxylamine or N-oxides (nitrones) and thiosynergists such as distearyl thiodipropionate or dilauryldithiopropionate.

Examples of suitable hindered amines are 1,1-bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (l, 2,2,6,6-pentamethyl-4-piperidyl) sebazate, bis (l octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (l, 2,2,6, 6-pentamethyl-4-piperidyl) -n-butyl-3,5-di-tert- butyl 4-hydroxybenzyl malonate, the

Condensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic

Condensation products of N, N'-bis (2, 2,6,6-tetramethyl-4-piperidyl

) hexamethylenediamine and 4-tert-octylamino-2,6-di-chloro-l, 3,5-triazine, tris (2, 2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2, 2.6 , 6-tetra-methyl-4-piperidyl) -l, 2,3,4-butanetetracarboxylate, 1,1'-l, 2-ethanediyl-bis (3,5,5-tetramethylpiperazinone), 4- Benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, linear or cyclic condensation products of N, N'-bis (2,2,6,6-tetramethyl-4-) piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4 oxospiro- [4,5] decane and epichlorohydrin.

Suitable dispersants are, for example:

Polyacrylates, e.g. B. copolymers with long-chain side groups, polyacrylate block copolymers, alkylamides: z. N, N'-l, 2-ethanediyl-bisoctadecanamide,

Sorbitan esters, e.g. As monostearyl sorbitan esters, titanates and zirconates, reactive copolymers with functional groups z. For example, polypropylene-co-acrylic acid,

Polypropylene co-maleic anhydride or polyethylene co-glycidyl methacrylate Typical applications of the invention flame-retardant plastics are in the electrical / electronics industry, transport and construction, furniture and textile industry z. In the form of injection molded parts, films or films,

Coatings or lacquers, foams, fibers, cables, profiles, tapes and pipes, adhesives produced by extrusion, injection molding, blow molding, calendering, pressing, spinning or coating, dipping and coating processes.

The incorporation of the above-described flame retardants and the additional additives in the plastic is carried out by conventional processing methods, whereby preferably the polymer is melted and mixed with the flame retardants and optionally other additives, preferably by mixers, kneaders and extruders. As processing machines are preferred extruders such. B.

Single-screw extruder, twin-screw extruder, planetary roller extruder,

Ring extruders, co-kneaders, which are preferably equipped with a vacuum degassing. The processing can be carried out under air or under inert gas conditions if necessary. Various flame retardants and additives can be added separately or as a mixture in the form of

Liquids, powders, flakes, flakes, granules or compacted products or also in the form of masterbatches or concentrates.

The present invention will be further illustrated by the following non-limiting examples.

The synthesis of the heptazine derivatives used in the following was carried out according to DE 102004047257. In an analogous manner, the melamine, melamine and melon derivatives can be prepared.

Examples

Example 1: Synergistic action of the invention

Compositions when used as flame retardants for

Polypropylene. The extrusions of the polypropylene samples (DOW C766-03) are made at a temperature of 190 ° C and a screw speed of 150 rpm on a DSM Micro 5cc twin-screw extruder. The residence time of the mixture in bypass operation is 60 s. The desired mixture of polymer and additives is first mixed manually in a beaker and fed in small portions to the micro-extruder. If the volume of the device is filled with melt, the material remains in the device for a further 60 s (dwell time) and is then drained off.

The resulting plastic strands are granulated (Pell-Tec SD 50 pure).

Test specimens for the fire test are produced from the granules at a temperature of 220 ° C and a pressure of 2 t on a hydraulic 10 t press (Werner & Pfleiderer). For this purpose, the granules are filled into the mold and these transferred into the already preheated press. At a pressure of 0.5 t, the granules are first melted for 60 seconds. When the melting time has elapsed, the pressure is increased to 2 t and kept constant for a further 3 min. While maintaining the contact pressure, the mold is cooled to 60 ° C and then removed the sample body. The specimens are in accordance with the standard

 following dimensions: 127.5 x 12.5 x 1.5 mm.

The inventive examples contained in Table 1 and

 Comparative examples were tested according to DIN EN 60695-11-10 and the

 Burning times and classification according to standard obtained:

Table 1: Compositions in polypropylene (example: 7H DPE) and

 Results of the fire test

Example Composition Firing Classification Note

 Flame retardant Sum of the according to DIN EN

 Afterburning times 60695-11-10

 of 5 test pieces

 at 2

 flame applications

 according to standard

 [in seconds]

 Comparative Example 1 25% HZD 96 V-2

Comparative Example 2 20% HZD 113 V-2 *

 Sample is already burning

Comparative Example 3 5% dicumyl * Not

 classifies the first

 Flame completely off

 16% HZD + according to the invention

 25V-2

Example 1 4% dicumyl

 18% HZD + according to the invention

 32V-2

Example 2 2% dicumyl

 16% HZD + according to the invention

 34 V-2

Example 3 4% Polycumyl

 HZD = Phosphorus-containing heptazine derivative of the formula Ia, where R = -O-phenyl

 Dicumyl and polycumyl were purchased from United Initiators GmbH & Co KG Germany

The inventive examples surprisingly have significantly shorter firing times compared to the comparative examples at the same concentration. In addition, a comparison of Comparative Example 1 with the

 Examples 1 and 2 according to the invention that the inventive

 Compositions even when reducing the total amount of

 Flame retardant (25% total content of flame retardant in

 Comparative Example 1 against 20% total amount of the flame retardant in Examples 1 and 2 according to the invention) to a strong reduction of

 Burning times leads (25 s in the inventive example 1 and 32 s im

 Inventive Example 2 versus 96 s in Comparative Example 1). The

 Comparative Example 3 proves that the radical generator used alone has no effect as a flame retardant, since the specimens already burn completely at the first flame.

Examples 4-7:

 In a manner analogous to Example 1 according to the invention, dicumyl was replaced by distearyl disulfide (Hostanox SE 10, manufacturer: Clariant SE) (Example 4),

 2-mercaptobenzothiazole (obtained from Aldrich Germany) (Example 5) or

Azodicarbonamid (Example 6, obtained from Aldrich Germany, deviating at a pressing temperature of 200 ° C made) replaced. Analogously to Example 1 according to the invention, a derivative with R =-naphthyl was used instead of HZD (Example 7). In all cases, shorter burn times are obtained.

Claims

claims A composition comprising asymmetric and symmetrical phosphorus-containing heptazine derivatives represented by the formula (1), asymmetrical and symmetrical phosphorus-containing melamine derivatives represented by the formula (Ia), unsymmetrical and symmetrical ones  phosphorus-containing melam derivatives (1,3,5-triazines-2,4,6-triamines-n - (4,6-diamino-l, 3,5-triazine-2-yl) represented by the formula (lb)) , and / or unsymmetrical and symmetrical phosphorus-containing melon derivatives (poly [8-amino-1,3,4,6,7,9,9b-heptaazaphenalene-2,5-diyl) imino] represented by the formula (Ic))

(Formula 1))

(Formula (2))

(Formula (3)) and / or

(Formula (4)) wherein, in the formula (1c), n = 2 to 100, where R _a , R _b , R _c and R _{d are} independently an azide group - N ₃ or a -N = PR _! R ₂ R ₃ group, with the proviso that at least one radical of R _a , R _b and R _{c is} a -N = PRiR ₂ R ₃ group, wherein Ri, R ₂ , and R _{3 are} independently a radical, selected from the group a consisting of a straight or branched (Ci-Ci ₂₎ -alkyl, (C ₃ -C ₇₎ cycloalkyl radical, a straight or branched chain (Ci-Ci ₂₎ alkenyl radical, a straight or branched (Ci-Ci ₂₎ alkoxy radical, furyl, furanyl, benzofuranyl, thienyl, thiazolyl, benzothiazolyl, thiadiazolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyrazinyl, benzothienyl, morpholinyl, thiomorpholinyl, piperidinyl, piperazinyl, pyrrolidinyl, Pyrimidinyl, imidazolinyl, pyrazolidinyl, phenyl, Phenoxy, benzyl, benzyloxy, naphthyl, naphthoxy, di (C ₁ -C ₆ ) alkylamino, tri (C ₁ -C ₆ ) alkylsilyl or pyridyl each having one to five substituents independently selected from the group consisting of β a straight-chain or branched-chain (d C ₆ ) alkyl, a (C ₃ -C ₇ ) cycloalkyl, a straight or branched chain (Ci-C ₆ ) alkenyl, a straight or branched chain (Ci-C ₆ ) alkoxy, halogen, hydroxy, amino, di (C ₁ -C ₆ ) alkylamino, nitro, cyano, benzyl, 4-methoxybenzyl, 4-nitrobenzyl, phenyl, and 4-methoxyphenyl, and oligomers and polymers derived therefrom; (B) at least one compound from the group of  Radical generators. 2. Composition according to claim 1,  d a d u r c h e c e n c i n e s that  the phosphorus-containing heptazine derivative (a) a phosphorus-containing  Heptazine derivative according to formula (Ib),

(Formula (Ib)) wherein R _1; R ₂ , and R ₃ independently represent a radical selected from the group a, consisting of a straight-chain or branched-chain (Ci-Ci ₂ ) -alkyl radical, a (C ₃ -C ₇ ) -cycloalkyl radical, a straight-chain or branched-chain (Ci -C ₂₎ alkenyl, a straight or branched (Ci-Ci ₂₎ alkoxy, furyl, furanyl, benzo furanyl, thienyl, thiazolyl, benzothiazolyl, thiadiazolyl, imidazolyl,  Pyrazolyl, triazolyl, tetrazolyl, pyrazinyl, benzothienyl, morpholinyl, thiomorpholinyl, piperidinyl, piperazinyl, pyrrolidinyl, pyrimidinyl, Imidazolinyl, pyrazolidinyl, phenyl, phenoxy, benzyl, benzyloxy, naphthyl, naphthoxy, di (Ci-C ₆₎ alkylamino, tri (C ₁ -C ₆₎ alkylsilyl or pyridyl, which are each independently selected from one to five substituents selected from the group β consisting of a straight-chain or branched-chain (C ₁ -C ₆ ) -alkyl radical, a (C ₃ -C ₇ ) -cycloalkyl radical, a straight-chain or branched-chain (C ₁ -C ₆ ) -alkenyl radical, a straight-chain or branched-chain (C ₁ -C ₆ ) -alkenyl radical C ₆ ) alkoxy, halogen, hydroxy, amino, di (C 1 -C ₆ ) alkylamino, nitro, cyano, benzyl, 4-methoxybenzyl, 4-nitrobenzyl, phenyl, and 4-methoxyphenyl, may be substituted and oligomers derived therefrom and polymers. 3. Composition according to claim 1 or 2, characterized in that the phosphorus-containing heptazine derivative (a) is a phosphorus-containing heptazine derivative according to formula (lb), where Ri, R ₂ and R _{3 are} each -O-phenyl (phenoxy) or m-kresyloxy, -1-naphthyloxy or 2-naphthyloxy or 2-biphenyloxy or 4-biphenyloxy. 4. Composition according to at least one of the preceding  Claims,  d a d u rc h e ke n ze i c h n et that  the at least one compound from the group of radical generators (b) comprises one or more compounds having at least one of the following functional groups:  -N = N- (azo group)  -NH-HN- (hydrazine)  > C = N-NH- (hydrazone)  > C = N-N = C <(azine)  -N = N-N <(triazene)  -S-S- (disulfide, polysulfide)  -S-H (thiol)  thiuram sulfide  dithiocarbamate  mercaptobenzothiazole  Sulfenamide. 5. Composition according to at least one of the preceding  Claims,  d a d u rch e ke n ze i c h n et that the at least one compound (b) from the group of Radical generators comprises at least one compound from the group of CC radical generators. 6. Composition according to at least one of the preceding  Claims,  d a d u r c h e n c i n e c e n s that  the at least one compound (b) from the group of  Radical generators at least one compound from the group of Radical generators which decompose thermally induced above 180 ° C. 7. Composition according to at least one of the preceding  Claims,  d a d u r c h e n c i n e s that  the at least one compound (b) from the group of  Radical generators the connection Dicumyl (CAS No. 1889-67-4, Formula 5)

and or umyl-1,4 (CAS No. 25822-43-9, Formula

 where n = 2-1000, preferably 2-20 and / or Polycumyl-1,3 where n = 2-1000, preferably 2-20, includes. 8. Composition according to at least one of the preceding  Claims,  d a d u r c h e n c i n e c e n s that  the compound (b) from the group of radical generators  Dicumyl (CAS No. 1889-67-4, Formula 5)

is. 9. Composition according to at least one of the preceding  Claims,  d a d u r c h e n c i n e s that  the compound (b) from the group of radical generators  Polycumyl (CAS No. 25822-43-9, Formula 6)

where n = 2-1000, preferably 2-20. 10. Material composition comprising 99 to 50, in particular 95 to 70, wt.% Of a polymer and 1 to 50, in particular 5 to 30, wt.% Of a composition according to any one of claims 1 to 8. 11. Material composition according to claim 10,  d a d u r c h e n c i n e s that the polymer is selected from the group consisting of: a) polymers of olefins or diolefins such. As polyethylene (LDPE, LLDPE, VLDPE, MDPE, HDPE), metallocene PE (m-PE), polypropylene, polyisobutylene, poly-4-methyl-pentene-l, polybutadiene, polyisoprene, polycyclooctene, and copolymers in the form of statistical  Gradient or block structures such. Polypropylene-polyethylene (EP), EPM or EPDM, ethylene-vinyl acetate (EVA), ethylene-acrylic ester; b) polystyrene, polymethylstyrene, styrene-butadiene, styrene-butadiene-styrene (SBS), styrene-isoprene, styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile-acrylate (ASA) styrene-maleic anhydride polymers including corresponding graft copolymers such as z. Styrene on butadiene or maleic anhydride on SBS; c) halogen-containing polymers such. B. polyvinyl chloride and  polyvinylidene chloride; d) polymers of unsaturated esters such. For example, polyacrylates and  Polymethacrylates such as PMMA, polyacrylonitrile; e) polymers of unsaturated alcohols and derivatives, such as. B.  Polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral; f) polyacetals, such as. For example, polyoxymethylene; g) polyphenylene oxides and blends with polystyrene; h) polyurethanes, in particular linear polyurethanes; i) polyamides such as. As polyamide-6, 6.6., 6.10. 4.6, 6.12, 12.12., Polyamide 11, polyamide 12 and (partially) aromatic polyamides such. B. polyphthalamide; j) polyimides, polyamideimides, polyetherimides, polyketones, polysulfones, polyethersulfones, polyphenylene sulfide. k) polyesters such. For example, polyethylene terephthalate and polybutylene terephthalate, polylactic acid; I) polycarbonate; m) cellulose derivatives such. B. cellulose nitrate, cellulose acetate,  cellulose propionate; n) and mixtures, combinations or blends of two or more of the aforementioned polymers. 12. Material composition, in addition to the compositions  according to claim 1-9 still further additives from the group of UV absorbers, light stabilizers, stabilizers, hydroxylamines, benzofuranones, metal deactivators, Füllstoffdesaktivatoren, nucleating agents, impact modifiers, plasticizers, lubricants, rheology modifiers, processing aids, pigments, dyes , optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, dispersants,  Contains compatibilizers, oxygen scavengers, acid scavenger, marking agents, antifogging agents and / or flame retardants. 13. A composition of matter according to claim 12, which comprises one or more Flame retardant comprises, selected from a) inorganic flame retardants, in particular Al (OH) _{3 /} Mg (OH) ₂ , AIO (OH), phyllosilicates in particular montmorillonite, and / or organically modified, double salts, in particular Mg-Al silicates MgC0 ₃ , huntite , Hydromagnesite or halloysite, and Sb ₂ 0 ₃ , Sb ₂ 0 ₅ , MoO ₃ , zinc stannate, zinc hydroxystannate; b) nitrogen-containing flame retardants, in particular melamine, melem, melam, melon, melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, allantoin, phosphacenes esp.  Melamine cyanurate, melamine phosphate, melamine pyrophosphate, Dimelamine phosphate, melamine polyphosphate, ammonium polyphosphate, melamine borate, melamine hydrobromide; c) phosphorus-containing flame retardants, in particular red phosphorus,  Phosphates, in particular resorcinol diphosphate, bisphenol A diphosphate and their oligomers, triphenyl phosphate, phosphinates, in particular salts of hypophosphorous acid and their derivatives, such as  Diethylaluminum phosphinate or aluminum phosphinate,  Aluminum phosphonate, aluminum phosphite, phosphonate esters, oligomeric and polymeric derivatives of methane phosphonic acid, 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO) and substituted compounds; d) chlorine and bromine-containing compounds, in particular polybrominated  Diphenyloxides, tris (3-bromo-2,2-bis (bromomethyl) propyl phosphate, ethylene bis (tetrabromophthalimide), tetrabromo-bisphenol A, brominated polystyrene, brominated polybutadiene, brominated epoxy resin, Polypentabromobenzyl acrylate, polypentabromobenzyl acrylate in combination with Sb ₂ 0 ₃ and / or Sb ₂ 0 _5; e) borates, in particular zinc borate or calcium borate; f) anti-drip agents, in particular polytetrafluoroethylene. 14. Material composition according to claim 11,  d a d u rch e ke n ze i c h n et that  the polymer comprises one or more polyolefins, in particular polyethylene, polypropylene, copolymers or blends of ethylene and propylene,  Polystyrene and / or one or more polyurethanes. Use of a composition according to at least one of  previous claims as flame retardants, in particular for plastics in the form of injection-molded parts, films, coatings,  Foams, fibers, cables and pipes. 16. Process for producing a flame-retardant plastic,  d a d u rch e ke n ze i c h n et that  a plastic is added to a composition according to any one of claims 1-9.