HK1245014B - Flame retardant mixtures and the production and use thereof - Google Patents

Description

Flame retardant mixture, its preparation and use

Technical Field

The present invention relates to a flame retardant mixture, its preparation and its use.

Background Art

According to the prior art, salts of dialkylphosphinic acid (also called dialkylphosphinic salts) are used in the form of their Mg salts, Ca salts, Al salts, Sb salts, Sn salts, Ge salts, Ti salts, Fe salts, Zr salts, Zn salts, Ce salts, Bi salts, Sr salts, Mn salts, Li salts, Na salts and K salts in flame retardant mixtures.

Flame retardant mixtures according to the prior art have limited heat resistance. They are effective within a limited temperature range within which the starting materials consisting of polymer, flame retardant, glass fibers, and other additives can be compounded to form flame-retardant polymer molding materials. The term "processing window" is used to define a lower and upper temperature range.

The lower temperature limit is derived from the specific temperature at which the toughness of the polymer is low enough so that it is conveyable and mixable in the machine.

The upper temperature limit is indirectly manifested in the decomposition of components and the subsequent weathering of decomposition products when flame-retardant polymer molding materials and polymer moldings are stored under humid conditions. If the polymer decomposes, the mechanical strength properties (elastic modulus, flexural strength, elongation at break) of the flame-retardant polymer moldings decrease.

Summary of the Invention

The object of the present invention is therefore to provide a heat-resistant flame retardant mixture having a broad processing window.

The object is achieved by adding iron to salts of diorganophosphinic acid, in particular dialkylphosphinic acid.

Surprisingly, it has been found that the flame retardant mixtures according to the invention have a broadened processing window during the compounding of flame-retardant polymer molding materials or during the injection molding of flame-retardant polymer moldings and simultaneously exhibit a good flame-retardant effect.

The present invention therefore relates to flame retardant mixtures comprising as component A) 99.9999 to 87% by weight of diorganophosphinate and as component B) 0.0001 to 13% by weight of iron, the sum of A) and B) being 100% by weight.

The iron can be present as iron itself, ie in the form of a simple substance. Preferably, however, the iron is present in the form of a substance containing iron, ie as an iron compound or an iron alloy.

DETAILED DESCRIPTION

The present invention therefore also relates to a flame retardant mixture comprising, as component A), 99.9999 to 75% by weight of a diorganophosphinate and, as component B), 0.0001 to 13% by weight of iron in the form of an iron-containing substance B1), wherein the amount of B1) is 0.0001 to 25% by weight and wherein the sum of A) and B1) is 100% by weight.

Preferably, the diorganophosphinate corresponds to formula (II)

in,

R ¹ and R ² are identical or different and represent linear, branched or cyclic C ₁ -C ₁₈ -alkyl, C ₆ -C ₁₈ -aryl, C ₇ -C ₁₈ -arylalkyl and/or C ₇ -C ₁₈ -alkylaryl,

m represents 1 to 4, and

M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na and/or K.

Surprisingly, it has been found that the flame retardant mixtures according to the invention have a broadened processing window during the compounding of flame-retardant polymer molding materials or during the injection molding of flame-retardant polymer moldings while exhibiting a good flame-retardant effect.

Preferably, in formula (II), R ¹ and R ² are identical or different and independently represent methyl, ethyl, n-propyl, isopropyl, butyl, n-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl (isopentyl), 3-methylbutan-2-yl, 2-methylbutan-2-yl, 2,2-dimethylpropyl (neopentyl), hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclopentylethyl, cyclohexyl, cyclohexylethyl, phenyl, phenylethyl, methylphenyl and/or methylphenylethyl.

In particular, the flame retardant mixture comprises 99.999-98% by weight of component A) and 0.001-2% by weight of component B).

Preferably, in the flame retardant mixture according to the invention, component B1) is present in the form of iron(II) dialkylphosphinate, iron(III) dialkylphosphinate, iron(II) monoalkylphosphinate, iron(III) monoalkylphosphinate, iron(II) alkylphosphonate, iron(III) alkylphosphonate, iron(II) alkylphosphonate, iron(III) alkylphosphonate, iron(II) phosphite, iron(III) phosphite, iron(II) phosphate and/or iron(III) phosphate.

Particularly preferably, in the flame retardant mixture according to the invention, component B1) is present in the form of bis(diethylphosphinate) iron(II) and/or tris(diethylphosphinate) iron(III), bis(dipropylphosphinate) iron(II) and/or tris(dipropylphosphinate) iron(III), bis(butylethylphosphinate) iron(II) and/or tris(butylethylphosphinate) iron(III), bis(n-butylethylphosphinate) iron(II) and/or tris(n-butylethylphosphinate) iron(III), bis(sec-butylethylphosphinate) iron(II) and/or tris(sec-butylethylphosphinate) iron(III), bis(hexylethylphosphinate) iron(II) and/or or tris(hexylethylphosphinate)iron(III), bis(dibutylphosphinate)iron(II) and/or tris(dibutylphosphinate)iron(III), bis(hexylbutylphosphinate)iron(II) and/or tris(hexylbutylphosphinate)iron(III), bis(octylethylphosphinate)iron(II) and/or tris(octylethylphosphinate)iron(III), bis(ethyl(cyclopentylethyl)phosphinate)iron(II) and/or tris(ethyl(cyclopentylethyl)phosphinate)iron(III), bis(butyl(cyclopentylethyl)phosphinate)iron(II) and/or tris(butyl(cyclopentylethyl)phosphinate)iron(III), bis(ethyl(cyclohexylethyl)phosphinate)iron(II) and/or tris(butyl(cyclopentylethyl)phosphinate)iron(III), Iron (II) and/or tris(ethyl(cyclohexylethyl)phosphinate) iron (III), bis(butyl(cyclohexylethyl)phosphinate) iron (II) and/or tris(butyl(cyclohexylethyl)phosphinate) iron (III), bis(ethyl(phenylethyl)phosphinate) iron (II) and/or tris(ethyl(phenylethyl)phosphinate) iron (III), bis(butyl(phenylethyl)phosphinate) iron (II) and/or tris(butyl(phenylethyl)phosphinate) iron (III), bis(ethyl(4-methylphenylethyl)phosphinate) iron (II) and/or tris(ethyl(4-methylphenylethyl)phosphinate) iron (III), Iron (II) bis(butyl(4-methylphenylethyl)phosphinate) and/or iron (III) tri(butyl(4-methylphenylethyl)phosphinate), iron (II) bis(butylcyclopentylphosphinate) and/or iron (III) tri(butylcyclopentylphosphinate), iron (II) bis(butylphenylphosphinate) and/or iron (III) tri(butylphenylphosphinate), iron (II) bis(ethyl(4-methylphenyl)phosphinate) and/or iron (III) tri(ethyl(4-methylphenyl)phosphinate), and/or iron (II) bis(butyl(4-methylphenyl)phosphinate) and/or iron (III) tri(butyl(4-methylphenyl)phosphinate);

Iron (II) and/or iron (III) mono(ethylphosphinate), iron (II) and/or iron (III) mono(propylphosphinate), iron (II) and/or iron (III) mono(propylphosphinate), iron (II) and/or iron (III) mono(butylphosphinate), iron (II) and/or iron (III) mono(n-butylphosphinate), iron (II) and/or iron (III) mono(n-butylphosphinate), iron (II) and/or iron (III) mono(sec-butylphosphinate), iron (II) and/or iron (III) mono(hexylphosphinate), and/or iron (III) mono(octylphosphinate). The present invention is present in the form of iron (II) mono(octylphosphinate) iron (III); iron (II) ethylphosphonate and/or iron (III) ethylphosphonate, iron (II) propylphosphonate and/or iron (III) propylphosphonate, iron (II) butylphosphonate and/or iron (III) butylphosphonate, iron (II) n-butylphosphonate and/or iron (III) n-butylphosphonate, iron (II) sec-butylphosphonate and/or iron (III) sec-butylphosphonate, iron (II) hexylphosphonate and/or iron (III) hexylphosphonate, and/or iron (II) octylphosphonate and/or iron (III) octylphosphonate.

Particularly preferably, components A) and B1) are present in the form of a physical mixture.

Preferably, the flame retardant mixture according to the invention comprises 60 to 99.8999% by weight of component A), 0.0001 to 20% by weight of component B1) and 0.1 to 40% by weight of further components C), wherein the sum of components A), B1) and C) is 100% by weight, with the proviso that components A), B1) and C) are each different compounds.

Preferably, components A), B1) and C) are present in the form of a physical mixture.

Preferably, components A) and C) form identical compounds with one another and are present in a physical mixture with component B1).

Component C) is a telomer of formula (III)

H-(C _w H _2w ) _k P(O)(OM)(C _x H _2x ) _l -H (III)

wherein in formula (III), independently of one another,

k represents 1 to 9, l represents 1 to 9, w represents 2 to 9, x represents 2 to 9, and

M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and/or a protonated nitrogenous base,

and the groups (C _w H _2w ) _k , (C _x H _2x ) _l may be linear or branched;

and/or the telomer is a telomer of formula (I)

in,

R ³ , R ⁴ are identical or different and represent C ₆ -C ₁₀ -arylene, C ₇ -C ₂₀ -alkylarylene, C ₇ -C ₂₀ -arylalkylene and/or C ₃ -C ₁₆ -cycloalkyl or C ₃ -C ₁₆ -bicycloalkyl,

M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and/or a protonated nitrogenous base,

And wherein components A) and C) are different compounds.

Particularly preferably, in formula (III), w and x each represent 2 or 3, and k and l each represent 1 to 3, and M represents Al, Ti, Fe or Zn.

Preferably, the telomer is a metal salt of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid, ethyloctylphosphinic acid, sec-butylethylphosphinic acid, 1-ethylbutyl-butylphosphinic acid, ethyl-1-methylpentyl-phosphinic acid, di-sec-butylphosphinic acid (di-1-methyl-propylphosphinic acid), propyl-hexylphosphinic acid, dihexylphosphinic acid, hexyl-nonylphosphinic acid, propyl-nonylphosphinic acid, dinonylphosphinic acid, dipropylphosphinic acid, butyl-octylphosphinic acid, hexyl-octylphosphinic acid, dioctylphosphinic acid, ethyl(cyclopentylethyl)phosphinic acid, butyl(cyclopentylethyl)phosphinic acid, The present invention also provides a novel phosphinic acid salt comprising: 1, 2, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 59, 65, 67, 68, 69, 71, 72, 73, 74, 75, 76, 77, 78, 79, 81, 82, 83, 84, 85, 86, 87, 88, 79, 81, 82

Preferably, the flame retardant mixture according to the invention further comprises a synergist as component D), wherein the synergist is melamine phosphate, dimelamine phosphate, pentamelamine triphosphate, trimelamine diphosphate, tetramelamine triphosphate, hexamelamine pentaphosphate, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melem polyphosphate and/or melon polyphosphate; is a melamine condensation product such as melam, melem and/or melon; is an oligoester of tris(hydroxyethyl)isocyanurate with an aromatic polycarboxylic acid, benzoguanamine, tris(hydroxyethyl)isocyanurate, allantoin, glycoluril, melamine, melamine cyanurate, urea cyanurate, dicyandiamide and/or guanidine; is a compound of the formula (NH ₄ ) _y H _3-y PO ₄ or (NH ₄ PO ₃ ) a nitrogen-containing phosphate of _z , wherein y is equal to 1 to 3 and z is equal to 1 to 10,000; an aluminum phosphite, an aluminum pyrophosphite, an aluminum phosphonate, an aluminum pyrophosphonate; a silicate, a zeolite, silica, a ceramic powder, a zinc compound such as zinc borate, zinc carbonate, zinc stannate, basic zinc stannate, zinc phosphate, zinc sulfide, zinc oxide, zinc hydroxide, tin oxide hydrate, basic zinc silicate, zinc molybdate, magnesium hydroxide, hydrotalcite, magnesium carbonate and/or calcium magnesium carbonate.

Preferably, in this case the flame retardant mixture comprises

a) 0.0001 to 99.7999% by weight of component A),

b) 0.0001 to 99.7999% by weight of component B1),

c) 0.1 to 40% by weight of component C), and

d) 0.1 to 40% by weight of component D),

The sum of a), b), c) and d) is 100% by weight, provided that components A), B1) and C) are different compounds.

Preferably, the flame retardant mixture has a particle size of 0.01 to 1000 μm, a bulk density of 50 to 1500 g/l, a tamped density of 100 to 1100 g/l, a stacking angle of 5 to 45 degrees, a BET surface area of 1 to 40 m ² /g, an L-color value of 85 to 99.9, an a-color value of -4 to +9, and a b-color value of -2 to +6.

Particularly preferably, the flame retardant mixture has a particle size of 0.5 to 800 μm, a bulk density of 80 to 800 g/l, a tamped density of 600 to 800 g/l, and a stacking angle of 10 to 40 degrees.

The present invention also relates to the following items:

1. A flame retardant mixture comprising, as component A), 99.9999 to 0.0001% by weight of a dialkylphosphinate and, as component B), 0.0001 to 13% by weight of iron, the sum of a) and b) being 100% by weight.

2. The flame retardant mixture according to claim 1, comprising as component A) 99.9999 to 75% by weight of a diorganophosphinate and as component B) 0.0001 to 13% by weight of iron in the form of an iron-containing substance B1), wherein the amount of B1) is 0.0001 to 25% by weight and the sum of A) and B1) is 100% by weight.

3. The flame retardant mixture according to item 1 or 2, characterized in that the dialkylphosphinate corresponds to formula (II)

in,

R ¹ and R ² are identical or different and represent linear, branched or cyclic C ₁ -C ₁₈ -alkyl, C ₆ -C ₁₈ -aryl, C ₇ -C ₁₈ -arylalkyl and/or C ₇ -C ₁₈ -alkylaryl,

m represents 1 to 4, and

M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na and/or K.

4. The flame retardant mixture according to any one or more of items 1 to 3, characterized in that in formula (II), R ¹ and R ² are identical or different and independently of one another represent methyl, ethyl, n-propyl, isopropyl, butyl, n-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl (isopentyl), 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl (neopentyl), hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclopentylethyl, cyclohexyl, cyclohexylethyl, phenyl, phenylethyl, methylphenyl and/or methylphenylethyl.

5. The flame retardant mixture according to any one or more of items 1 to 4, characterized in that it comprises 99.9995 to 95% by weight of component A) and 0.0005 to 5% by weight of component B).

6. The flame retardant mixture according to any one or more of items 1 to 5, characterized in that component B1) is present in the form of iron(II) dialkylphosphinate, iron(III) dialkylphosphinate, iron(II) monoalkylphosphinate, iron(III) monoalkylphosphinate, iron(II) alkylphosphonate, iron(III) alkylphosphonate, iron(II) alkylphosphonate, iron(III) phosphite, iron(III) phosphite, iron(II) phosphate and/or iron(III) phosphate.

7. The flame retardant mixture according to any one or more of items 1 to 6, characterized in that component B1) is composed of bis(diethylphosphinate) iron(II) and/or tris(diethylphosphinate) iron(III), bis(dipropylphosphinate) iron(II) and/or tris(dipropylphosphinate) iron(III), bis(butylethylphosphinate) iron(II) and/or tris(butylethylphosphinate) iron(III), bis(n-butylethylphosphinate) iron(II) and/or tris(n-butylethylphosphinate) iron(III), bis(sec-butylethylphosphinate) iron(II) and/or tris(sec-butylethylphosphinate) iron(III), bis(hexylethylphosphinate) iron(II) and/or tris(hexylethylphosphinate) iron(III). Iron (III) (hexylethylphosphinate), iron (II) (dibutylphosphinate) and/or iron (III) (dibutylphosphinate), iron (II) (hexylbutylphosphinate) and/or iron (III) (hexylbutylphosphinate), iron (II) (octylethylphosphinate) and/or iron (III) (octylethylphosphinate), iron (II) (ethyl(cyclopentylethyl)phosphinate), iron (II) (ethyl(cyclopentylethyl)phosphinate), iron (II) (butyl(cyclopentylethyl)phosphinate), iron (II) (tributyl(cyclopentylethyl)phosphinate), iron (III) (ethyl(cyclohexylethyl)phosphinate), and/or iron (II) (tributyl(cyclopentylethyl)phosphinate). Iron (III) tris(ethyl(cyclohexylethyl)phosphinate), iron (II) bis(butyl(cyclohexylethyl)phosphinate) and/or iron (III) tris(butyl(cyclohexylethyl)phosphinate), iron (II) bis(ethyl(phenylethyl)phosphinate) and/or iron (III) tris(ethyl(phenylethyl)phosphinate), iron (II) bis(butyl(phenylethyl)phosphinate) and/or iron (III) tris(butyl(phenylethyl)phosphinate), iron (II) bis(ethyl(4-methylphenylethyl)phosphinate) and/or iron (III) tris(ethyl(4-methylphenylethyl)phosphinate), iron (II) bis(butyl(4-methylphenylethyl)phosphinate) and/or iron (III) tris( Iron (III) butyl(4-methylphenylethyl)phosphinate), iron (II) bis(butylcyclopentylphosphinate) and/or iron (III) tri(butylcyclopentylphosphinate), iron (II) bis(butylcyclohexylethylphosphinate) and/or iron (III) tri(butylcyclohexylethylphosphinate), iron (II) bis(butylphenylphosphinate) and/or iron (III) tri(butylphenylphosphinate), iron (II) bis(ethyl(4-methylphenyl)phosphinate) and/or iron (III) tri(ethyl(4-methylphenyl)phosphinate), and/or iron (II) bis(butyl(4-methylphenyl)phosphinate) and/or iron (III) tri(butyl(4-methylphenyl)phosphinate);

Iron(II)mono(ethylphosphinate) and/or iron(III)mono(ethylphosphinate), iron(II)mono(propylphosphinate) and/or iron(III)mono(propylphosphinate), iron(II)mono(butylphosphinate) and/or iron(III)mono(butylphosphinate), iron(II)mono(n-butylphosphinate) and/or iron(III)mono(n-butylphosphinate), iron(II)mono(sec-butylphosphinate) and/or iron(III)mono(sec-butylphosphinate), iron(II)mono(hexylphosphinate) and/or iron(III)mono(hexylphosphinate), and/or iron(II)mono(octylphosphinate) and/or iron(III)mono(octylphosphinate);

Iron (II) and/or iron (III) ethylphosphonate, iron (II) and/or iron (III) propylphosphonate, iron (II) and/or iron (III) butylphosphonate, iron (II) and/or iron (III) n-butylphosphonate, iron (II) and/or iron (III) n-butylphosphonate, iron (II) and/or iron (III) sec-butylphosphonate, iron (II) and/or iron (III) hexylphosphonate, and/or iron (II) and/or iron (III) octylphosphonate;

The following iron(II) salts and/or iron(III) salts: ethyl(cyclopentylethyl)phosphinic acid, butyl(cyclopentylethyl)phosphinic acid, ethyl(cyclohexylethyl)phosphinic acid, butyl(cyclohexylethyl)phosphinic acid, ethyl(phenylethyl)phosphinic acid, butyl(phenylethyl)phosphinic acid, ethyl(4-methylphenylethyl)phosphinic acid, ethylphenylphosphinic acid, butyl(4-methylphenylethyl)phosphinic acid, butylcyclopentylphosphinic acid, butylcyclohexylethylphosphinic acid, butylphenylphosphinic acid, ethyl(4-methylphenyl)phosphinic acid, butyl(4-methylphenyl)phosphinic acid, ethylphosphinylacetic acid and/or ethylphosphinylbutyric acid, hydroxymethylethyl-ethylphosphinic acid, 1-hydroxy- The phosphinyl group may be present in the form of 1-methylpropyl-ethylphosphinic acid, butyl-ethylphosphonate, acylethylphosphonic anhydride, butyl-ethylphosphonic acid, butylethylphosphinic acid, ethylphosphinylisobutyronitrile (1-cyano-1-methylethyl-ethylphosphinic acid), propylethylphosphinic acid, tert-butyl-ethylphosphonate, tert-butyl-ethylphosphinic acid, hydroxymethylbutyl-ethylphosphinic acid, 3-hydroxy-3-methylpentyl-ethylphosphinic acid, propoxyethyl-ethylphosphinic acid, phenylethyl-ethylphosphinic acid, 2-ethylphosphinylethyl-laurate, ethylpentylphosphinic acid, tert-butoxyethyl-ethylphosphinic acid, ethylphosphinylisocapronitrile, hexylethylphosphinic acid and/or ethylphosphinylethyl sulfate.

8. The flame retardant mixture according to any one or more of items 1 to 7, characterized in that components A) and B1) are present in the form of a physical mixture.

9. The flame retardant mixture according to any one or more of items 1 to 8, characterized in that it comprises 60 to 99.8999% by weight of component A), 0.0001 to 20% by weight of component B1) and 0.1 to 40% by weight of a further component C), wherein the sum of components A), B1) and C) is 100% by weight, provided that components A), B1) and C) are each different compounds.

10. The flame retardant mixture according to any one or more of items 1 to 9, characterized in that components A), B) and C) are present in the form of a physical mixture with one another.

11. The flame retardant mixture according to any one or more of items 1 to 10, characterized in that components A) and C) form identical compounds with one another and are present in a physical mixture with component B).

12. The flame retardant mixture according to any one or more of items 1 to 11, characterized in that component C) is a telomer of formula (III)

H-(C _w H _2w ) _k P(O)(OM)(C _x H _2x ) _l -H (III)

wherein in formula (III), independently of one another,

k represents 1 to 9, l represents 1 to 9, w represents 2 to 9, x represents 2 to 9, and

M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and/or a protonated nitrogenous base,

and the groups (C _w H _2w ) _k , (C _x H _2x ) _l may be linear or branched;

and/or the telomers are those of formula (I)

in

R ³ , R ⁴ are identical or different and represent C ₆ -C ₁₀ -arylene, C ₇ -C ₂₀ -alkylarylene, C ₇ -C ₂₀ -arylalkylene and/or C ₃ -C ₁₆ -cycloalkyl or C ₃ -C ₁₆ -bicycloalkyl,

M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and/or a protonated nitrogenous base; components A), B1) and C) are different compounds.

13. Flame retardant mixture according to any one or more of items 1 to 12, characterized in that, in formula (VI), w and x each represent 2 or 3, k and l each represent 1 to 3, and M represents Al, Ti, Fe or Zn.

14. The flame retardant mixture according to any one or more of items 1 to 13, characterized in that the telomer is a metal salt of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid, ethyloctylphosphinic acid, sec-butylethylphosphinic acid, 1-ethylbutyl-butylphosphinic acid, ethyl-1-methylpentylphosphinic acid, di-sec-butylphosphinic acid (di-1-methylpropylphosphinic acid), propyl Hexylphosphinic acid, dihexylphosphinic acid, hexyl-nonylphosphinic acid, propyl-nonylphosphinic acid, dinonylphosphinic acid, dipropylphosphinic acid, butyl-octylphosphinic acid, hexyl-octylphosphinic acid, dioctylphosphinic acid, ethyl (cyclopentylethyl)phosphinic acid, butyl (cyclopentylethyl)phosphinic acid, ethyl (cyclohexylethyl)phosphinic acid, butyl (cyclohexylethyl)phosphinic acid, ethyl (phenylethyl)phosphinic acid, butyl (phenylethyl)phosphinic acid, ethyl ethylphosphinylisobutyronitrile (1-cyano-1-methylethyl-ethylphosphinic acid), propylethylphosphinic acid, hydroxymethylbutyl-ethylphosphinic acid, 3-hydroxy-3-methylpentyl-ethylphosphinic acid, propoxyethyl-ethylphosphinic acid, phenylethyl-ethylphosphinic acid, ethylpentylphosphinic acid, tert-butoxyethyl-ethylphosphinic acid, ethylphosphinylisocapronitrile, hexylethylphosphinic acid and/or ethylphosphinylethylsulfate/salt, wherein the metal of the metal salt is derived from Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na and/or K.

15. Flame retardant mixtures according to any one or more of items 1 to 14, characterized in that they further comprise as component D) a synergist, wherein the synergist is melamine phosphate, dimelamine phosphate, pentamelamine triphosphate, trimelamine diphosphate, tetramelamine triphosphate, hexamelamine pentaphosphate, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melem polyphosphate and/or melon polyphosphate; is a melamine condensation product such as melam, melem and/or melon; is an oligoester of tris(hydroxyethyl)isocyanurate with an aromatic polycarboxylic acid, benzoguanamine, tris(hydroxyethyl)isocyanurate, allantoin, glycoluril, melamine, melamine cyanurate, urea cyanurate, dicyandiamide and/or guanidine; is a compound of the formula (NH ₄ ) _y H _3-y PO ₄ or (NH ₄ PO ₃ ) _z nitrogen-containing phosphate, wherein y is equal to 1 to 3 and z is equal to 1 to 10,000; is aluminum phosphite, aluminum pyrophosphite, aluminum phosphonate, aluminum pyrophosphonate; is silicate, zeolite, silica, ceramic powder, zinc compound, such as zinc borate, zinc carbonate, zinc stannate, basic zinc stannate, zinc phosphate, zinc sulfide, zinc oxide, zinc hydroxide, tin oxide hydrate, basic zinc silicate, zinc molybdate, magnesium hydroxide, hydrotalcite, magnesium carbonate and/or calcium magnesium carbonate.

16. The flame retardant mixture according to item 16, characterized in that it comprises

a) 0.0001 to 74.8% by weight of component A),

b) 0.0001 to 25% by weight of component B1),

c) 0.1 to 40% by weight of component C), and

d) 0.1 to 40% by weight of component D),

The sum of A), B1), C) and D) is 100% by weight, provided that A), B1) and C) are different compounds.

17. Flame retardant mixture according to any one or more of items 1 to 16, characterized in that it has a particle size of 0.01 to 1000 μm, a bulk density of 50 to 1500 g/l, a tamped density of 100 to 1100 g/l, a stacking angle of 5 to 45 degrees, a BET surface area of 1 to 40 m ² /g, an L-color value of 85 to 99.9, an a-color value of -4 to +9, and a b-color value of -2 to +6.

18. The flame retardant mixture according to any one or more of items 1 to 17, characterized in that it has a particle size of 0.5 to 800 μm, a bulk density of 80 to 800 g/l, a tamped density of 600 to 800 g/l, and a stacking angle of 10 to 40 degrees.

19. Process for preparing a flame retardant mixture according to any one or more of items 1 to 18, characterized in that

a) in process stage 1, 0.9 to 1.1 molecules of olefin are added per P of a water-soluble salt of hypophosphorous acid or of the acid itself,

b) in process stage 2, adding an additional 0.9 to 1.1 molecules of olefin per P on the intermediate product from a) to the dialkylphosphinic acid or its salt,

c) in process stage 3, adding 1 to 9 further olefin molecules to 0 to 20% of the dialkylphosphinic acid molecules from process stage 1, thereby forming a telomer, wherein, if dialkylphosphinic acid is produced, it is converted into the corresponding salt,

d) in process stage 4, crystallization of the intermediate product from b) and/or c) and the metal salt is carried out,

e) In process stage 5, the iron compound/component B is admixed.

20. Process for preparing a flame retardant mixture according to any one or more of items 1 to 18, characterized in that

a) in process stage 1, from 0.9 to 1.1 molecules of olefin are added per water-soluble salt of hypophosphorous acid or per P on the acid itself,

b) in process stage 2, adding an additional 0.9 to 1.1 molecules of olefin per P on the intermediate product from a) to the dialkylphosphinic acid or its salt,

c) in process stage 3, adding 1 to 9 further olefin molecules to 0.1 to 20% of the dialkylphosphinic acid molecules from process stage 1, thereby forming a telomer, wherein, if dialkylphosphinic acid is produced, it is converted into the corresponding salt,

d) in process stage 4, a coprecipitation of the intermediate product from c) and the metal salt is carried out, and

e) In process stage 5, the iron compound/component B is admixed.

21. Process for preparing a flame retardant mixture according to any one or more of items 1 to 18, characterized in that

a) in process stage 1, from 0.9 to 1.1 molecules of olefin are added per water-soluble salt of hypophosphorous acid or per P on the acid itself,

b) in process stage 2, adding an additional 0.9 to 1.1 molecules of olefin, calculated per P on the intermediate product from a), to the dialkylphosphinic acid or its salt, wherein, if dialkylphosphinic acid is formed, it is converted into the corresponding salt,

c) in process stage 3, a coprecipitation of the intermediate product from b) and an iron salt is carried out, and

d) In process stage 4, the telomer/component C is admixed.

22. Process for preparing a flame retardant mixture according to any one or more of items 1 to 18, characterized in that

a) in process stage 1, from 0.9 to 1.1 molecules of olefin are added per water-soluble salt of hypophosphorous acid or per P on the acid itself,

b) in process stage 2, adding an additional 0.9 to 1.1 molecules of olefin, calculated per P on the intermediate product from a), to the dialkylphosphinic acid or its salt, wherein, if dialkylphosphinic acid is formed, it is converted into the corresponding salt,

c) in process stage 3, crystallization of the intermediate product from b) and the metal salt is carried out,

d) in process stage 4, optionally admixing a telomer, and

e) In process stage 5, the iron compound/component B is admixed.

23. The method according to any one or more of items 19 to 22, characterized in that as iron compounds and/or iron salts, there are used those having anions of the seventh main group; those having anions of oxoacids of the seventh main group; those having anions of the sixth main group; those having anions of oxoacids of the sixth main group; those having anions of the fifth main group; those having anions of oxoacids of the fifth main group; those having anions of oxoacids of the fourth main group; those having anions of oxoacids of the third main group; those having anions of pseudohalides; those having anions of oxoacids of transition metals. anions; those with organic anions from the group consisting of monocarboxylic acids, dicarboxylic acids, oligocarboxylic acids, polycarboxylic acids, acetic acid, trifluoroacetic acid, propionate, butyrate, valerate, octanoate, oleate, stearate, oxalic acid, tartaric acid, citric acid, benzoic acid, salicylate, lactic acid, acrylic acid, maleic acid, succinic acid, amino acids, acidic hydroxyl functions, p-phenolsulfonate, hydrated p-phenolsulfonate, hydrated acetylacetonate, tannate, dimethyldithiocarbamate, trifluoromethanesulfonate, alkylsulfonates and/or aralkylsulfonates; iron as elemental substance; iron as its fluoride, chloride, bromide, iodide, iodate, perchlorate, oxide, hydroxide, peroxide, superoxide, sulfate, bisulfate, hydrated sulfate, sulfite, persulfate, nitride, phosphide, nitrate, hydrated nitrate, nitrite, phosphate, superphosphate, phosphite, hypophosphite, pyrophosphate, carbonate, bicarbonate, basic carbonate, hydrated carbonate, silicate, hexafluorosilicate, hydrated hexafluorosilicate, stannate, borate, polyborate, perborate, thiocyanate, cyanate, cyanide, chromate, chromite, molybdate, permanganate, formate, acetate, hydrated Iron compounds are present in the form of acetates, hydrated trifluoroacetates, propionates, butyrates, valerates, octanoates, oleates, stearates, oxalates, tartrates, citrates, basic citrates, hydrated citrates, benzoates, salicylates, lactates, hydrated lactates, acrylic acid, maleic acid, succinic acid, glycine, phenolates, p-phenolsulfonates, hydrated p-phenolsulfonates, hydrated acetylacetonates, tannates, dimethyldithiocarbamates, trifluoromethanesulfonates, alkylsulfonates and/or aralkylsulfonates; and/or are used as alloys of iron with copper, tin, nickel, chromium, molybdenum, tungsten, vanadium.

24. The method according to any one or more of items 19 to 23, characterized in that initiators, free radical initiators, photoinitiators, inhibitors, free radical control agents, nucleating agents, co-crystallization agents, crystallization agents, strong electrolytes, wetting agents, solvents, acids, alkalis, alkaline compounds, strongly alkaline solutions, flow aids, bleaching agents, coupling agents, adhesion promoters, release agents, plastic additives, coating additives and flame retardants are added in the process stage and are coated with the flame retardant mixture according to at least one of items 1 to 9.

25. Use of the flame retardant mixture according to any one or more of items 1 to 18 as an intermediate for further syntheses, as a binder, as a crosslinker or accelerator in the curing of epoxy resins, polyurethanes and unsaturated polyester resins, as a polymer stabilizer, as a plant protection agent, as a chelating agent, as a mineral oil additive, as a corrosion inhibitor, in detergent and cleaning agent applications and in electronic applications; as a flame retardant, as a flame retardant for varnishes and foam-type coatings, as a flame retardant for wood and other cellulose-containing products, as a reactive and/or non-reactive flame retardant for polymers, for the production of flame-retardant polymer moldings, for the production of flame-retardant polymer moldings and/or for imparting flame retardancy to polyester and pure and blended cellulose textiles by impregnation.

26. Flame-retardant thermoplastic or thermosetting polymer molding materials, polymer moldings, polymer films, polymer filaments and polymer fibers, comprising 0.5 to 50% by weight of the flame retardant mixture according to one or more of items 1 to 18, 0.5 to 95% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55% by weight of additives and 0 to 70% by weight of fillers or reinforcing materials, wherein the sum of the components is 100% by weight, and wherein the polymer is a thermoplastic polymer of the HI (high impact) polystyrene, polyphenylene oxide, polyamide, polyester, polycarbonate type and blends or polymer blends of the ABS (acrylonitrile butadiene styrene) or PC/ABS (polycarbonate/acrylonitrile butadiene styrene) or PPE/HIPS (polyphenylene oxide/HI polystyrene) plastic type and/or a thermosetting polymer of the formaldehyde-phenol resin polymer, epoxide-phenol resin polymer, melamine-phenol resin polymer, unsaturated polyester, epoxy resin and/or polyurethane type.

27. The thermoplastic or thermosetting polymer molding material, polymer molding, polymer film, polymer filament and polymer fiber according to item 26, characterized in that it contains other additives, wherein the other additives are antioxidants, UV stabilizers, gamma ray stabilizers, hydrolysis stabilizers, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact modifiers, dyes, pigments, etc.

The present invention also relates to a method for preparing a flame retardant mixture according to any one or more of items 1 to 19, characterized in that

a) in process stage 1, 0.9 to 1.1 molecules of olefin are added per P of a water-soluble salt of hypophosphorous acid or of the acid itself,

b) in process stage 2, adding an additional 0.9 to 1.1 molecules of olefin per P on the intermediate product from a) to the dialkylphosphinic acid or its salt,

c) in process stage 3, adding 1 to 9 further olefin molecules to 0 to 20% of the dialkylphosphinic acid molecules from process stage 1, thereby forming a telomer, wherein, if dialkylphosphinic acid is produced, it is converted into the corresponding salt,

d) in process stage 4, crystallization of the intermediate product from b) and/or c) and the metal salt is carried out,

e) In process stage 5, the iron compound/component B is admixed.

The present invention also relates to a process for preparing a flame retardant mixture according to one or more of items 1 to 19, characterized in that

a) in process stage 1, from 0.9 to 1.1 molecules of olefin are added per water-soluble salt of hypophosphorous acid or per P on the acid itself,

b) in process stage 2, adding an additional 0.9 to 1.1 molecules of olefin per P on the intermediate product from a) to the dialkylphosphinic acid or its salt,

c) in process stage 3, adding 1 to 9 further olefin molecules to 0.1 to 20% of the dialkylphosphinic acid molecules from process stage 1, thereby forming a telomer, wherein, if dialkylphosphinic acid is produced, it is converted into the corresponding salt,

d) in process stage 4, a coprecipitation of the intermediate product from c) and the metal salt is carried out, and

e) In process stage 5, the iron compound/component B is admixed.

The present invention also relates to a further method for preparing a flame retardant mixture according to any one or more of items 1 to 19, characterized in that

a) in process stage 1, from 0.9 to 1.1 molecules of olefin are added per water-soluble salt of hypophosphorous acid or per P on the acid itself,

b) in process stage 2, adding an additional 0.9 to 1.1 molecules of olefin, calculated per P on the intermediate product from a), to the dialkylphosphinic acid or its salt, wherein, if dialkylphosphinic acid is formed, it is converted into the corresponding salt,

c) in process stage 3, a coprecipitation of the intermediate product from b) and an iron salt is carried out, and

d) In process stage 4, the telomer/component C is admixed.

Finally, the present invention relates to a process for preparing a flame retardant mixture according to any one or more of items 1 to 19, characterized in that

a) in process stage 1, from 0.9 to 1.1 molecules of olefin are added per water-soluble salt of hypophosphorous acid or per P on the acid itself,

b) in process stage 2, adding an additional 0.9 to 1.1 molecules of olefin, calculated per P on the intermediate product from a), to the dialkylphosphinic acid or its salt, wherein, if dialkylphosphinic acid is formed, it is converted into the corresponding salt,

c) in process stage 3, crystallization of the intermediate product from b) and the metal salt is carried out,

e) in process stage 4, optionally admixing a telomer, and

f) In process stage 5, the iron compound/component B is admixed.

Preferably, in the case of the above-mentioned method, as iron compounds and/or as iron salts, use is made of those having anions of the seventh main group; those having anions of oxoacids of the seventh main group; those having anions of the sixth main group; those having anions of oxoacids of the sixth main group; those having anions of the fifth main group; those having anions of oxoacids of the fifth main group; those having anions of oxoacids of the fourth main group; those having anions of oxoacids of the third main group; those having anions of pseudohalides; those having anions of oxoacids of transition metals; those having anions from the following: organic anions of monocarboxylic acids, dicarboxylic acids, oligocarboxylic acids, polycarboxylic acids, acetic acid, trifluoroacetic acid, propionate, butyrate, valerate, octanoate, oleate, stearate, oxalic acid, tartaric acid, citric acid, benzoic acid, salicylate, lactic acid, acrylic acid, maleic acid, succinic acid, amino acids, acidic hydroxyl groups, p-phenolsulfonate, hydrated p-phenolsulfonate, hydrated acetylacetonate, tannate, dimethyldithiocarbamate, trifluoromethanesulfonate, alkylsulfonate and/or aralkylsulfonate; iron as elemental substance; iron as fluoride, chloride, bromide, iodide, iodate Salt, perchlorate, oxide, hydroxide, peroxide, superoxide, sulfate, bisulfate, hydrated sulfate, sulfite, persulfate, nitride, phosphide, nitrate, hydrated nitrate, nitrite, phosphate, superphosphate, phosphite, hypophosphite, pyrophosphate, carbonate, bicarbonate, basic carbonate, hydrated carbonate, silicate, hexafluorosilicate, hydrated hexafluorosilicate, stannate, borate, polyborate, perborate, thiocyanate, cyanate, cyanide, chromate, chromite, molybdate, permanganate, formate, acetate, hydrated acetate, Iron compounds are present in the form of hydrated trifluoroacetate, propionate, butyrate, valerate, octanoate, oleate, stearate, oxalate, tartrate, citrate, basic citrate, hydrated citrate, benzoate, salicylate, lactate, hydrated lactate, acrylic acid, maleic acid, succinic acid, glycine, phenolate, p-phenolsulfonate, hydrated p-phenolsulfonate, hydrated acetylacetonate, tannate, dimethyldithiocarbamate, triflate, alkylsulfonate and/or aralkylsulfonate; and/or are used as alloys of iron with copper, tin, nickel, chromium, molybdenum, tungsten, vanadium.

Preferably, in the case of the above-described process, as metal salts, those with cations from the group of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na and/or K and the same anions as in the case of iron compounds are used and/or are used in the form of iron salts.

Preferably, in the case of the above-described method according to any one or more of items 20 to 25, initiators, free radical initiators, photoinitiators, inhibitors, free radical control assistants, nucleating agents, co-crystallization assistants, crystallization assistants, strong electrolytes, wetting agents, solvents, acids, alkalis, alkaline compounds, strongly alkaline solutions, flow aids, bleaching agents, coupling agents, adhesion promoters, release agents, plastic additives, coating additives and flame retardants are added in the corresponding process stages, which are encapsulated by the flame retardant mixture according to at least one of items 1 to 19.

The invention also relates to the use of the flame retardant mixture according to any one or more of items 1 to 19 as an intermediate for further syntheses, as a binder, as a crosslinker or accelerator in the curing of epoxy resins, polyurethanes and unsaturated polyester resins, as a polymer stabilizer, as a plant protection agent, as a chelating agent, as a mineral oil additive, as a corrosion inhibitor, in detergent and cleaning agent applications and in electronic applications.

In particular, the present invention relates to the use of the flame retardant mixture according to any one or more of items 1 to 19 as a flame retardant, as a flame retardant for varnishes and foam-type coatings, as a flame retardant for wood and other cellulose-containing products, as a reactive and/or non-reactive flame retardant for polymers, for the production of flame-retardant polymer moldings, for the production of flame-retardant polymer moldings and/or for imparting flame retardancy to polyesters and pure and blended cellulose fabrics by impregnation.

The present invention also includes flame-retardant thermoplastic or thermosetting polymer molding materials, polymer moldings, polymer films, polymer filaments and polymer fibers, which contain 0.5 to 45% by weight of the flame retardant mixture according to any one or more of items 1 to 19, 0.5 to 95% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55% by weight of additives and 0 to 55% by weight of fillers or reinforcing materials, where the sum of the components is 100% by weight.

Here, thermoplastic polymers are thermoplastic polymers of the HI (high impact) polystyrene, polyphenylene ether, polyamide, polyester, polycarbonate type and ABS (acrylonitrile butadiene styrene) or PC/ABS (polycarbonate/acrylonitrile butadiene styrene) or PPE/HIPS (polyphenylene ether/HI polystyrene) plastic type or polymer blends, and thermosetting polymers are thermosetting polymers of the formaldehyde-phenol resin polymer, epoxide-phenol resin polymer, melamine-phenol resin polymer, unsaturated polyester, epoxy resin and/or polyurethane type.

Preferably, the thermoplastic or thermosetting polymer molding materials, polymer moldings, polymer films, polymer filaments and polymer fibers contain further additives, wherein the further additives here are antioxidants, UV stabilizers, gamma stabilizers, hydrolysis stabilizers, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact modifiers, dyes, pigments and the like.

Preferred diorganophosphinates are dialkylphosphinates, which likewise correspond to formula (II).

Preferred dialkylphosphinates are especially those of the formula (II) in which R ¹ and R ² are identical or different and represent linear, branched or cyclic C ₁ -C ₁₈ -alkyl.

Preference is given to diethylphosphinate, where the cation used for salt formation is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na or K, and from these Al, Ti and Zn are again particularly preferred.

Preferred flame retardant mixtures are characterized in that they comprise 99.9999 to 80% by weight of component A) and 0.0001 to 20% by weight of component B1).

In particular, the flame retardant mixture comprises 99.9995 to 95% by weight of component A) and 0.0005-5% by weight of component B1).

Preference is given to flame retardant mixtures comprising 99.9999 to 80% by weight of component A) and 0.0001 to 20% by weight of iron (component B).

Particular preference is given to flame retardant mixtures comprising 99.9995 to 95% by weight of component A) and 0.0005 to 5% by weight of iron (component B).

Telomers are formed when olefins are added to hypophosphorous acid. Not only two molecules of olefin, but more, are added to the dialkylphosphinic acid. One or two alkyl chains are thus extended by one or more further olefin units.

Preferred telomers are those of formula (IV)

H-(C _w H _2w ) _k P(O)(OMe)(C _x H _2x ) _l -H (IV)

wherein in formula (V), independently of one another,

k represents 1 to 9, l represents 1 to 9, w represents 2 to 9 and x represents 2 to 9, and Me represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na and/or K.

Preferably, the telomer is present in the form of an Al salt, a Ti salt, a Fe salt and/or a Zn salt.

Preferably, in formula (VI), w and x also each represent 2 to 4, and k and l each represent 1 to 4.

When ethylene is used as olefin in the preparation of the dialkylphosphinic acid salts according to the invention, telomers of the type of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid, ethyloctylphosphinic acid etc. and/or their salts are preferably produced.

In the case of propylene, the order is significant.

Preferred olefins are ethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene and 1-octene.

The stereochemistry also allows the formation of branched alkyl chains, such as sec-butylethylphosphinate, 1-ethylbutyl-butyl-phosphinate, ethyl-1-methylpentylphosphinate, di-sec-butylphosphinate (di-1-methylpropylphosphinate), and the like.

Telomers themselves are phosphorus-containing compounds. Their content is given as a percentage of all phosphorus-containing components (P%). It is determined by means of ³¹ P-NMR.

The iron is preferably present in the form of an iron salt or iron compound and is physically mixed with component A). By the process according to the invention, it is homogeneously mixed with the dialkylphosphinate or dialkylphosphinate-telomer salt mixture.

Preferably, the iron salts and iron compounds used for preparing the physically mixed flame retardant mixtures according to the invention are iron(II) and/or iron(III) salts.

Preferably, the iron salt is an iron (II) salt and/or an iron (III) salt with the following: inorganic anions (halides) of the seventh main group, such as fluoride, chloride, bromide, iodide; anions of oxygen-containing acids of the seventh main group (hypohalites, halites, halides such as iodate, perhalates such as perchlorate); anions of the sixth main group (sulfur compounds), such as oxygen, hydroxide, peroxide, superoxide; anions of oxygen-containing acids of the sixth main group (sulfate, hydrogen sulfate, hydrated sulfate, sulfite, persulfate); anions of the fifth main group (phosphorus compounds), such as nitrogen ions, phosphorus ions; anions of oxygen-containing acids of the fifth main group (nitrate, hydrated nitrate, nitrite, phosphate, superphosphate, phosphite, hypophosphite, pyrophosphate); anions of oxygen-containing acids of the fourth main group (carbonate, bicarbonate, basic carbonate, hydrated carbonate, silicate, hexafluorosilicate, hydrated hexafluorosilicate, stannate); anions of oxygen-containing acids of the third main group (borate, polyborate, perborate); anions of pseudohalides (thiocyanate, cyanate, cyanide); anions of oxygen-containing acids of transition metals (chromate, chromite, molybdate, permanganate).

Preferably, the iron salt is an iron (II) salt and/or iron (III) salt with an organic anion selected from the group consisting of monocarboxylic acids, dicarboxylic acids, oligocarboxylic acids, polycarboxylic acids (formic acid salts (formates)), acetic acid (acetate, hydrated acetate), trifluoroacetic acid (hydrated trifluoroacetate), propionate, butyrate, valerate, octanoate, oleate, stearate, oxalic acid (oxalate), tartaric acid (tartrate), citric acid (citrate, alkaline citrate, hydrated citrate), benzoic acid (benzoate), salicylate, lactic acid (lactate, hydrated lactate), acrylic acid, maleic acid, succinic acid, amino acids (glycine), acidic hydroxyl functional groups (phenolate ions, etc.), p-phenolsulfonate, hydrated p-phenolsulfonate, hydrated acetylacetonate, tannate, dimethyldithiocarbamate, trifluoromethanesulfonate, alkylsulfonate and/or aralkylsulfonate.

Preferably, the iron salt is iron (II) borate and/or iron (III) borate, iron (II) sulfate and/or iron (III) sulfate, hydrated iron (II) sulfate and/or hydrated iron (III) sulfate, hydrated iron (II) hydroxy sulfate and/or hydrated iron (III) sulfate, mixed hydrated iron (II) sulfate and/or mixed hydrated iron (III) sulfate, sulfated iron (II) oxide and/or sulfated iron (III), iron (II) acetate and/or iron (III) acetate, iron (II) nitrate and/or iron (III) nitrate, Iron (II) fluoride and/or iron (III) fluoride, hydrated iron (II) fluoride and/or hydrated iron (III) fluoride, iron (II) chloride and/or iron (III) chloride, hydrated iron (II) chloride and/or hydrated iron (III) chloride, iron (II) oxychloride and/or iron (III) oxychloride, iron (II) bromide and/or iron (III) bromide, iron (II) iodide and/or iron (III) iodide, hydrated iron (II) iodide and/or hydrated iron (III) iodide, and/or iron (II) carbonate and/or iron (III) carbonate derivatives.

Preferably, the metal compound is iron (II) acetate and/or iron (III) acetate, iron (II) chloride and/or iron (III) chloride, iron (II) nitrate and/or iron (III) nitrate, iron (II) sulfate and/or iron (III) sulfate, iron (II) phosphinate and/or iron (III) phosphinate, monoalkyl iron (II) phosphinate and/or monoalkyl iron (III) phosphinate, and/or alkyl iron (II) phosphinate and/or alkyl iron (III) phosphinate.

The iron (component B) mentioned in item 1 is usually present in the form of an iron salt or iron compound (component B1). Preferred iron salts are monoalkylphosphinate iron(II), including ethylphosphinate iron(II), propylphosphinate iron(II), butylphosphinate iron(II), n-butylphosphinate iron(II), sec-butylphosphinate iron(II), hexylphosphinate iron(II), and/or octylphosphinate iron(II).

Preferred iron salts are monoalkyl iron(III) phosphinates, including iron(III) ethylphosphinate, iron(III) propylphosphinate, iron(III) butylphosphinate, iron(III) n-butylphosphinate, iron(III) sec-butylphosphinate, iron(III) hexylphosphinate, iron(III) hexylphosphinate and/or iron(III) octylphosphinate.

Preferred iron salts are iron(II) alkylphosphonates, including iron(II) ethylphosphonate, iron(II) propylphosphonate, iron(II) butylphosphonate, iron(II) n-butylphosphonate, iron(II) sec-butylphosphonate, iron(II) hexylphosphonate and/or iron(II) octylphosphonate.

Preferred iron salts are iron(III) alkylphosphonates, including iron(III) ethylphosphonate, iron(III) propylphosphonate, iron(III) butylphosphonate, iron(III) n-butylphosphonate, iron(III) sec-butylphosphonate, iron(III) hexylphosphonate and/or iron(III) octylphosphonate.

Preferred coprecipitated iron salts are dialkylphosphinate iron(II), including bis(diethylphosphinate)iron(II), bis(dipropylphosphinate)iron(II), bis(butylethylphosphinate)iron(II), bis(n-butylethylphosphinate)iron(II), bis(sec-butylethylphosphinate)iron(II), bis(hexylethylphosphinate)iron(II), bis(dibutylphosphinate)iron(II), bis(hexylbutylphosphinate)iron(II) and/or bis(octylethyl)phosphinate iron(II).

Preferred iron salts are iron(III) dialkylphosphinates, including iron(III) tris(diethylphosphinate), iron(III) tris(dipropylphosphinate), iron(III) tris(butylethylphosphinate), iron(III) tris(n-butylethylphosphinate), iron(III) tris(sec-butylethylphosphinate), iron(III) tris(hexylethylphosphinate), iron(III) tris(dibutylphosphinate), iron(III) tris(hexylbutylphosphinate) and/or iron(III) tris(octylethyl)phosphinate.

A low particle size is advantageous for the stability of the physically mixed flame retardant mixture according to the invention with respect to segregation upon shaking.

Particularly preferred are dialkylphosphinates of 0.01 to 1000 μm, dialkylphosphinate-telomer salt coprecipitates of 0.01 to 1000 μm, and average particle sizes d ₅₀ of the flame retardant mixtures according to the invention of 0.01 to 1000 μm.

Particular preference is given to dialkylphosphinates, dialkylphosphinate-telomer salt mixtures, and average particle sizes d ₅₀ of the flame retardant mixtures according to the invention of 0.1 to 90 μm.

In the process according to the invention, it is possible to add any type of auxiliary agent which achieves advantages in the production process or improves the product properties.

In the process according to the invention, one or more synergists may be admixed in one or more further process stages.

Preferably, the flame-retardant polymer molding material comprises 5 to 45% by weight of the flame retardant mixture according to the invention, 5 to 90% by weight of a polymer or a mixture thereof, 1 to 40% by weight of additives and 20 to 55% by weight of glass fibers.

Preferably, the polymer is derived from a thermoplastic polymer such as polyester, polystyrene or polyamide and/or a thermosetting polymer.

Preferably, the polymers are polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, poly-1-butene, poly-4-methyl-1-pentene, polyisoprene or polybutadiene, and polymers of cyclic olefins, for example cyclopentene or norbornene; furthermore polyethylene (which may optionally be crosslinked), for example high-density polyethylene (HDPE), high-density and high-molar-mass polyethylene (HDPE-HMW), high-density and ultra-high-molar-mass polyethylene (HDPE-UHMW), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), branched low-density polyethylene (VLDPE) and mixtures thereof.

Preferably, the polymer is a copolymer of a monoolefin and a diene with each other or with other vinyl monomers, such as ethylene propylene copolymer, linear low density polyethylene (LLDPE) and its mixture with low density polyethylene (LDPE), propylene-1-butene copolymer, propylene-isobutylene copolymer, ethylene-1-butene copolymer, ethylene-hexene copolymer, ethylene-methylpentene copolymer, ethylene-heptene copolymer, ethylene-octene copolymer, propylene-butadiene copolymer, isobutylene-isoprene copolymer, ethylene-alkyl acrylate copolymer, ethylene-alkyl methylacrylate copolymer, The present invention also includes copolymers of ethylene and propylene, ethylene-vinyl acetate copolymers and their copolymers with carbon monoxide, or ethylene-acrylic acid copolymers and their salts (ionomers), and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene norbornene; furthermore, mixtures of such copolymers with one another, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers, LDPE/ethylene-acrylic acid copolymers, LLDPE/ethylene-vinyl acetate copolymers, LLDPE/ethylene-acrylic acid copolymers and alternating or statistically structured polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

Preferably, the polymer is a hydrocarbon resin (eg C ₅ -C ₉ ), including hydrogenated versions thereof (eg tackifier resins) and mixtures of starch and polyalkylenes.

Preferably, the polymer is polystyrene (polystyrene 143E) (BASF), poly(p-methylstyrene), poly(α-methylstyrene).

Preferably, the polymer is a copolymer of styrene or α-methylstyrene with a diene or acrylic derivative, such as styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and styrene-butadiene-alkyl methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; a high-impact mixture of a styrene copolymer and another polymer such as a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; and a block copolymer of styrene, such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene/butylene-styrene or styrene-ethylene/propylene-styrene.

Preferably, the polymer is a graft copolymer of styrene or α-methylstyrene, for example styrene grafted onto polybutadiene, styrene grafted onto polybutadiene-styrene copolymer or polybutadiene-acrylonitrile copolymer, styrene and acrylonitrile (or methacrylonitrile) grafted onto polybutadiene; styrene, acrylonitrile and methyl methacrylate grafted onto polybutadiene; styrene and maleic anhydride grafted onto polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide grafted onto polybutadiene; styrene and maleimide grafted onto polybutadiene, styrene and alkyl acrylate or alkyl methacrylate grafted onto polybutadiene, styrene and acrylonitrile grafted onto ethylene-propylene-diene terpolymer, styrene and acrylonitrile grafted onto polyalkyl acrylate or polyalkyl methacrylate, styrene and acrylonitrile grafted onto acrylate-butadiene copolymer, and mixtures thereof, for example so-called ABS polymers, MBS polymers, ASA polymers or AES polymers.

Preferably, the polymer is a halogen-containing polymer, for example polychloroprene, chloroprene rubber, chlorinated and brominated copolymers from isobutylene-isoprene (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene with chlorinated ethylene, epichlorohydrin homopolymers and epichlorohydrin copolymers, in particular polymers from halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; and copolymers thereof, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.

Preferably, the polymer is a polymer derived from an α,β-unsaturated acid and its derivatives, such as polyacrylates and polymethacrylates, polymethyl methacrylate impact-modified with butyl acrylate, polyacrylamide and polyacrylonitrile, and copolymers of the above monomers with each other or with other unsaturated monomers, for example acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.

Preferably, the polymer is a polymer derived from an unsaturated alcohol and an amine or an acyl derivative or acetal thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine; and copolymers thereof with olefins.

Preferably, the polymer is a homopolymer or copolymer of a cyclic ether, such as polyalkylene glycol, polyethylene oxide, polypropylene oxide or a copolymer thereof with bisglycidyl ether.

Preferably, the polymer is a polyacetal, such as polyoxymethylene, and polyoxymethylene containing comonomers such as ethylene oxide; polyacetal modified with thermoplastic polyurethane, acrylate or MBS.

Preferably, the polymer is polyphenylene ether and polyphenylene sulfide and mixtures thereof with styrene polymers or polyamides.

Preferably, the polymers are polyurethanes derived from polybutadiene and polyesters, polyethers having terminal hydroxyl groups on the one hand, and from aliphatic or aromatic polyisocyanates on the other hand, and precursors thereof.

Preferably, the polymers are polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 2/12, polyamide 4 (poly-4-aminobutyric acid, 4, DuPont), polyamide 4/6 (poly(tetramethylene adipamide), poly(tetramethylene adipamide), 4/6, DuPont), polyamide 6 (polycaprolactam, poly-6-aminocaproic acid, 6, DuPont), K122, DSM; 7301, DuPont; B 29, Bayer), polyamide 6/6 ((poly(N,N'-hexamethylene adipamide), 6/6, DuPont, 101, DuPont; A30, AKV, AM, Bayer; A3, BASF), polyamide 6/9 (poly(hexamethylene azelaic acid), 6/9, DuPont), polyamide 6/10 (poly(hexamethylene sebacic acid), 6/10, DuPont), polyamide 6/12 (poly(hexamethylene dodecanedioic acid), 6/12, DuPont), polyamide 6/66 (poly(hexamethylene adipamide-co-caprolactam), 6/66, DuPont), polyamide 7 (poly-7-aminoheptanoic acid, 7, DuPont), polyamide 7,7 (polyheptamethylene pimelic acid, 7,7, DuPont), polyamide 8 (poly-8-aminooctanoic acid, 8, DuPont), polyamide 8,8 (polyoctamethylene suberamide, 8,8, DuPont), polyamide 9 (poly-9-aminononanoic acid, 9, DuPont), polyamide 9,9 (polynonamethylene azelaic acid, 9,9, DuPont), polyamide 10 (poly-10-aminodecanoic acid, 10, DuPont), polyamide 10,9 (poly(decamethylene azelaic acid), 10,9, DuPont), polyamide 10,10 (poly(decamethylene sebacic acid, 10,10, DuPont), polyamide 11 (poly-11-aminoundecanoic acid, 11, DuPont), polyamide 12 (polylauryl lactam, 12, DuPont, L20, Ems Chemie), aromatic polyamides from meta-xylene, diamines and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic acid and/or terephthalic acid and, optionally, elastomers as modifiers (polyhexamethylene isophthalamide, polyhexamethylene terephthalamide), for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide. Block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, for example polyethylene glycol, polypropylene glycol or polybutylene glycol; furthermore, polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing ("RIM-polyamide systems").

Aromatic polyamides such as PA4T, PA6T, PA9T, PA10T, PA11T and/or MXD6, amorphous polyamides such as "rigid" and "flexible" 6I/X and TPE-A may also be used.

Preferably, the polymer is polyurea, polyimide, polyamideimide, polyetherimide, polyesterimide, polyhydantoin and polybenzimidazole.

Preferably, the polymer is a polyester derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate (2500, 2002, Celanese; BASF), poly-1,4-dihydroxymethylcyclohexane terephthalate, polyhydroxybenzoates and block polyetheresters derived from polyethers having hydroxyl end groups; and polyesters modified with polycarbonate or MBS.

Preferably, the polymer is polycarbonate, polyester carbonate, polysulfone, polyethersulfone and polyetherketone.

Preferably, the thermosetting polymer is a formaldehyde-phenol resin polymer, an epoxide-phenol resin polymer, a melamine-phenol resin polymer and/or a polyurethane.

Preferably, the thermosetting polymer is epoxy resin.

Preferably, the thermosetting polymer is an epoxy resin cured with resols, phenols, phenol derivatives and/or dicyandiamide, alcohols and amines.

Preferably, the epoxide resin is a polyepoxide.

Preferably, the epoxy resin is selected from novolac and bisphenol A resin.

Preferably, the thermosetting polymer is an unsaturated polyester resin, a dicyclopentadiene-modified unsaturated polyester, a polyphenylene ether or a butadiene polymer; a block copolymer having a polybutadiene block or a polyisoprene block and a block from styrene or α-methylstyrene; a block copolymer having a first polybutadiene block and a second polyethylene block or an ethylene-propylene block; a block copolymer having a first polyisoprene block and a second polyethylene block or an ethylene-propylene block.

Preferably, the thermosetting polymers are those based on epoxidized vegetable oils (epoxidized soybean oil/linseed oil), acrylic acid derivatives (acrylic acid, crotonic acid, isocrotonic acid, methacrylic acid, cinnamic acid, maleic acid, fumaric acid, methyl methacrylate) and hydroxyalkyl acrylates and/or hydroxyalkyl alkylacrylates (hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, polyethylene glycol methacrylate).

Preferably, the thermosetting polymers are used in electrical switch parts, components in automotive construction, electrotechnical engineering, electronics, circuit boards, prepregs, potting compounds for electronic components, in ship and rotor blade construction, in GFK (glass fiber reinforced plastic) outdoor applications, household and sanitary applications, engineering materials and other products.

Preferably, the thermosetting polymer is an unsaturated polyester resin (UP resin) derived from copolyesters of saturated and unsaturated polycarboxylic acids, in particular dicarboxylic acids or their anhydrides, with polyols and vinyl compounds as crosslinkers.

UP resins cure by free-radical polymerization using initiators (eg peroxides) and accelerators.

Unsaturated polyesters may contain ester groups as linking compounds in the polymer chain.

Preferred unsaturated dicarboxylic acids and unsaturated dicarboxylic acid derivatives for preparing polyesters are maleic acid, maleic anhydride and fumaric acid, itaconic acid, citric acid, mesaconic acid, which may be mixed with up to 200 mol % of at least one aliphatic, saturated or cycloaliphatic dicarboxylic acid, based on the unsaturated acid component.

Preferred saturated dicarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, dihydrophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, adipic acid, succinic acid, sebacic acid, glutaric acid, methylglutaric acid, pimelic acid.

Preferred polyhydric, especially dihydric, optionally unsaturated alcohols are alkanediols and oxaalkanediols which generally have acyclic or cyclic groups.

Preferred unsaturated monomers copolymerizable with unsaturated polyesters preferably carry vinyl, vinylidene or allyl groups, such as preferably styrene, but also, for example, core-alkylated or core-alkenylated styrenes, where the alkyl group may contain 1 to 4 carbon atoms, such as vinyltoluene, divinylbenzene, α-methylstyrene, tert-butylstyrene; vinyl esters of carboxylic acids having 2 to 6 carbon atoms, preferably vinyl acetate, vinyl propionate, vinyl benzoate; vinylpyridine, vinylnaphthalene, vinylcyclohexane, acrylic acid and methacrylic acid and/or their esters having 1 to 4 carbon atoms in the alcohol component (preferably vinyl methyl esters); esters, allyl esters and methallyl esters), their amides and nitriles, maleic anhydride, maleic partial esters and maleic diesters having 1 to 4 carbon atoms in the alcohol component, maleic partial amides and maleic diamides or cyclic imides such as butyl acrylate, methyl methacrylate, acrylonitrile, N-methylmaleimide or N-cyclohexylmaleimide; allyl compounds such as allylbenzene and allyl esters such as allyl acetate, diallyl phthalate, diallyl isophthalate, diallyl fumarate, allyl carbonate, diallyl phthalate, diallyl carbonate, triallyl phosphate and triallyl cyanurate.

The preferred vinyl compound for crosslinking is styrene.

Preferred unsaturated polyesters may also carry ester groups in the side chains, such as polyacrylates and polymethacrylates.

A preferred curing agent system is a peroxide and an accelerator.

Preferred accelerators are metal coinitiators and aromatic amines and/or UV light and photosensitizers, for example benzoin ethers and azo catalysts such as azoisobutyronitrile, mercaptans such as lauryl mercaptan, bis-(2-ethylhexyl) sulfide and bis-(2-mercaptoethyl) sulfide.

The process for preparing the flame-retardant copolymers is characterized in that at least one ethylenically unsaturated dicarboxylic anhydride derived from at least one C ₄ -C ₈ -dicarboxylic acid, at least one vinylaromatic compound and at least one polyol are copolymerized and then reacted with the flame retardant mixture according to the invention.

Preferably, dicyclopentadiene-modified unsaturated polyesters can be used, which are obtained by reacting dicyclopentadiene, maleic anhydride, water, a saturated alcohol and optionally another polyacid. The polyester is crosslinked with a free radical polymerizable monomer such as styrene to form a resin.

Preferably, the polymer is a cross-linked polymer derived from an aldehyde or phenol, urea or melamine, such as phenol-formaldehyde resins, urea-formaldehyde resins and melamine-formaldehyde resins.

Preferably, the polymer is a crosslinkable acrylic resin derived from a substituted acrylate, for example from an epoxy acrylate, a urethane acrylate or a polyester acrylate.

Preferably, the polymer is an alkyd resin, a polyester resin, or an acrylate resin, which is crosslinked with a melamine resin, a urea-formaldehyde resin, an isocyanate, an isocyanurate, a polyisocyanate, or an epoxy resin.

Preferably, the polymer is a crosslinked epoxy resin derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, such as products of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, which are crosslinked by conventional curing agents such as anhydrides or amines, with or without accelerators.

Preferred thermosetting plastics are polymers from the class of cyanate esters, cyanate ester/bismaleimide copolymers, bismaleimide-triazine-epoxy resin blends and butadiene polymers.

Preferred butadiene polymers are block copolymers comprising 70-95 wt% of one or more monovinyl-substituted aromatic hydrocarbon compounds having 8-18 carbon atoms and 30-5 wt% of one or more conjugated dienes having 4-12 carbon atoms and optionally a crosslinker.

Preferably, the flame retardant mixture according to the invention is also used in resin systems consisting of polybutadiene resins or polyisoprene resins or mixtures thereof with unsaturated butadiene- or isoprene-containing polymers which can participate in crosslinking.

Preferably, the polymer is a crosslinked epoxy resin derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for example from bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, which is crosslinked by conventional curing agents and/or accelerators.

Suitable glycidyl compounds are bisphenol A diglycidyl ester, bisphenol F diglycidyl ester, polyglycidyl esters of phenol-formaldehyde resins and cresol-formaldehyde resins, polyglycidyl esters of phthalic acid, isophthalic acid and terephthalic acid and trimellitic acid, N-glycidyl compounds of aromatic amines and heterocyclic nitrogenous bases and diglycidyl and polyglycidyl compounds of polyhydric aliphatic alcohols.

Suitable curing agents are aliphatic, cycloaliphatic, aromatic and heterocyclic amines or polyamines, such as ethylenediamine, diethylenetriamine, triethylenetetramine, propane-1,3-diamine, hexamethylenediamine, aminoethylpiperazine, isophoronediamine, polyamidoamines, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenol sulfone, aniline-formaldehyde resins, 2,2,4-trimethylhexane-1,6-diamine, m-xylenediamine, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine), polyamidoamines, cyanoguanidine and dicyandiamide, Likewise, polyacids or their anhydrides, such as phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride, and phenols, such as phenol-novolak resins, cresol-novolak resins, dicyclopentadiene-phenol adduct resins, phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins, bisphenol-modified phenol aralkyl resins, phenol trimethylolmethane resins, tetrahydroxyphenylethane resins, naphthol-novolak resins, naphthol-phenol cocondensate resins, naphthol-cresol cocondensate resins, bisphenol-modified phenol resins and aminotriazine-modified phenol resins. All curing agents can be used individually or in combination with one another.

Suitable catalysts or promoters for crosslinking during polymerization are tertiary amines, benzyldimethylamine, N-alkylpyridines, imidazoles, 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, metal salts of organic acids, Lewis acids and amine complex salts.

Preferably, the polymer is a crosslinked polymer derived from aldehydes on the one hand and phenols, ureas or melamines on the other hand, such as phenol-formaldehyde resins, urea-formaldehyde resins and melamine-formaldehyde resins. Preferably, the polymer is a crosslinkable acrylic resin derived from substituted acrylates, for example from epoxy acrylates, urethane acrylates or polyester acrylates.

Preferred polyester polyols are obtained by polycondensation of polyols such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, methylpentanediol, 1,6-hexanediol, trimethylolpropane, glycerol, pentaerythritol, diglycerol, glucose and/or sorbitol with dibasic acids such as oxalic acid, malonic acid, succinic acid, tartaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid and/or terephthalic acid. These polyester polyols can be used alone or in combination.

Suitable polyisocyanates are aromatic, alicyclic and/or aliphatic polyisocyanates having not less than two isocyanate groups and mixtures thereof. Preferred are aromatic polyisocyanates such as toluene diisocyanate, methylene diphenyl diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, tri-4-isocyanatophenylmethane and polymethylene polyphenylene diisocyanate; alicyclic polyisocyanates such as methylene diphenyl diisocyanate, tolyl diisocyanate; aliphatic polyisocyanates and hexamethylene diisocyanate, isophorone diisocyanate, Demeryl diisocyanate, 1,1-methylenebis(4-isocyanatocyclohexane-4,4'-diisocyanatodicyclohexylmethane) isomer mixtures, 1,4-cyclohexyl diisocyanate, Bayer type and lysine diisocyanate, and mixtures thereof.

Suitable polyisocyanates are modified products which are obtained by reaction of polyisocyanates with polyols, ureas, carbodiimides and/or biuret.

Preferably, the polymer is an unsaturated polyester resin derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyols and vinyl compounds as crosslinking agents, as well as halogen-containing, flame-retardant versions thereof.

Preferably, the polymer is a cross-linkable acrylic resin derived from a substituted acrylate, such as an epoxy acrylate, a urethane acrylate or a polyester acrylate.

Preferably, the polymer is a mixture of the above polymers (polymer blend), such as PP/EPDM (polypropylene/ethylene-propylene-diene rubber), polyamide/EPDM or ABS (polyamide/ethylene-propylene-diene rubber or acrylonitrile-butadiene-styrene), PVC/EVA (polyvinyl chloride/ethylene vinyl acetate), PVC/ABS (polyvinyl chloride/acrylonitrile-butadiene-styrene), PVC/MBS (polyvinyl chloride/methacrylate-butadiene-styrene), PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene), PBTP/ABS (polybutylene terephthalate/acrylonitrile -Butadiene-styrene), PC/ASA (Polycarbonate/Acrylates-Styrene-Acrylonitrile), PC/PBT (Polycarbonate/Polybutylene Terephthalate), PVC/CPE (Polyvinyl Chloride/Chlorinated Polyethylene), PVC/Acrylate (Polyvinyl Chloride/Acrylate, POM/Thermoplastic PUR (Polyoxymethylene/Thermoplastic Polyurethane), PC/Thermoplastic PUR (Polycarbonate/Thermoplastic Polyurethane), POM/Acrylate (Polyoxymethylene/Acrylate), POM/MBS (Polyoxymethylene/Methacrylate-Butadiene-styrene), PPO/HIPS (Polyphenylene Oxide/High Impact Polystyrene), PPO/PA 6,6 (polyphenylene ether/polyamide 6,6) and copolymers, PA/HDPE (polyamide/high-density polyethylene), PA/PP (polyamide/polyethylene), PA/PPO (polyamide/polyphenylene ether), PBT/PC/ABS (polybutylene terephthalate/polycarbonate/acrylonitrile butadiene styrene) and/or PBT/PET/PC (polybutylene terephthalate/polyethylene terephthalate/polycarbonate).

Preferably, the prepared molding material has a rectangular shape with a regular or irregular base surface, a cubic shape, a cuboid shape, a pillow shape, or a prism shape.

The flame retardant mixtures according to the invention can also be used in elastomers such as nitrile rubber, nitrile rubber with carboxyl groups and carboxyl-terminated butadiene-acrylonitrile, chloroprene rubber, butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene rubber, butadiene rubber with acrylic resins and thermoplastic polyimides, urethane-modified copolyester polymers and other elastomers.

Preferred further additives in the flame retardant mixtures according to the invention are from the group of carbodiimides and/or (poly)isocyanates.

Preferred further additives are from the group consisting of sterically hindered phenols (eg OSP1), hindered amines and light stabilizers (eg HYDROXYLATE® 944, HYDROXYLATE® type), phosphinates and antioxidants (eg PEPQ from Clariant) and mold release agents (HYDROXYLATE® type from Clariant).

Preferred fillers in the flame retardant mixtures according to the invention are oxygen-containing compounds of silicon, magnesium compounds, for example metal carbonates of metals of the second main group of the periodic table, magnesium oxide, magnesium hydroxide, hydrotalcite, dihydrotalcite, magnesium carbonate or magnesium calcium carbonate, calcium compounds, for example calcium hydroxide, calcium oxide, hydrocalumite, aluminum compounds, for example aluminum oxide, aluminum hydroxide, boehmite, gibbsite or aluminum phosphate, red phosphorus, zinc compounds and/or aluminum compounds.

Preferred further fillers are glass beads.

Glass fibers are preferably used as reinforcement material.

Compounding apparatuses which can be used according to the invention are multi-zone screw extruders with a three-zone screw and/or a short compression screw.

Compounding apparatuses which can be used according to the invention are also, for example, Coperion Buss Compounding Systems, kneaders from CH-Pratteln, for example MDK/E46-11D and/or laboratory kneaders (MDK 46, L=11D from Buss, Switzerland).

Compounding equipment that can be used according to the invention is, for example, a twin-screw extruder from Coperion Werner & Pfleiderer GmbH & Co. KG, Stuttgart (ZSK 25, ZSK 30, ZSK 40, ZSK 58, ZSK MEGA compounders 40, 50, 58, 70, 92, 119, 177, 250, 320, 350, 380) and / or a twin-screw extruder from Berstorff GmbH, Hannover, LeistritzExtrusionstechnik GmbH, Nürnberg.

Compounding apparatuses that can be used according to the invention are, for example, annular extruders from 3+Extruder GmbH, which operate as a ring of three to twelve small screws rotating around a stationary core, and/or planetary roller extruders and/or vented extruders and/or cascade extruders and/or Maillefer screws, for example from Entex, Bochum.

Compounding apparatuses which can be used according to the invention are compounders with counter-rotating twin screws, for example the Compex 37 or 70 from Krauss-Maffei Berstorff.

The screw length (L) effective according to the invention is 20-40D in the case of a uniaxial extruder or a single-screw extruder; 8-48D in the case of a twin-screw extruder and, for example, 25D in the case of a multi-zone screw extruder, wherein the feed zone (L=10D), the transition zone (L=6D) and the discharge zone (L=9D) are 25D.

The present invention further relates to the use of the flame retardant mixture according to the invention as described in one or more of items 1 to 19 for use in or in plug connectors, current-carrying parts in power distributors (FI protection), circuit boards, potting compounds, power plugs, circuit breakers, lamp housings, LED housings, capacitor housings, coil bodies and ventilators, protective contacts, plugs, for use in or in circuit boards, plug housings, cables, flexible circuit boards, mobile phone charging cables, engine bonnets, textile coatings and other products.

This includes shaped bodies in the form of components for the electrical/electronic sector, in particular in the form of circuit boards, housings, foils, conductors, switches, distributors, relays, resistors, capacitors, coils, lamps, diodes, LEDs, transistors, connectors, regulators, memories and sensors, large-area components, in particular housing parts for switchgear, and elaborately designed components with demanding geometries.

Preferably, in the case of such a shaped body, the wall thickness is less than 0.5 mm, but can also be greater than 1.5 mm (up to 10 mm). Particularly suitable is less than 1.5 mm, more preferably less than 1 mm and particularly preferably less than 0.5 mm.

The flame retardant mixture according to the invention is preferably used together with glass fibers having an arithmetic mean length of 100 to 220 μm for producing flame-retardant polyamide molding materials and/or molded parts, wherein the production process for the polyamide molding material or molded part is adjusted so that the glass fibers in the resulting polyamide molding material or molded part have an arithmetic mean length in the range of 100 to 220 μm and the polyamide molding material or molded part is preferably classified as V-0 in accordance with IEC 60695-11-10 (UL94).

Preparation, processing and testing of flame-retardant polymer molding materials and polymer moldings.

The flame retardant component is mixed with the polymer pellets and any additives and added to PA 6,6 at 260-310°C or PA 6 at 250-275°C via a side feed of a twin-screw extruder (Leistritz ZSE 27/44D) at a temperature of 230 to 260°C (glass-fiber-reinforced PBT). The glass fibers are added via a second side feed. The homogenized polymer strands are removed, cooled in a water bath, and subsequently pelletized to form flame-retardant polymer molding materials.

After sufficient drying, the molding material is processed on an injection molding machine (Arburg 320C Allrounder) at a material temperature of 240-300° C. to give flame-retardant polymer moldings. These can be used as test pieces and tested and classified for flame retardancy according to the UL 94 test (Underwriter Laboratories).

The processing window of the PA GF30 compound was determined in an isothermal DSC experiment:

Flame-retardant polymer molding materials and flame-retardant polymer moldings were produced according to the general specifications described above. The composition was 49.7% by weight of polyamide (A27E01 from BASF SE), 30% by weight of glass fiber (PPG glass fiber HP 3610EC10 from PPG), 12.6% by weight of the flame retardant mixture according to the invention according to the examples, 6.6% by weight of melamine polyphosphate (MPP) (200/70 from BASF), 0.8% by weight of zinc borate (500 from RioTinto Minerals), and 0.3% by weight of wax (E Gran from Clariant).

Since the lower limit of the processing window is not affected, the decomposition of the flame-retardant polymer molding material at the upper limit is determined as a measure of the processing window. For this purpose, the weight loss at a defined temperature is used.

The weight loss in % by weight was determined in air at 330° C. after a holding time of 60 minutes using DSC (differential thermal analysis).

The flowability of the flame retardant mixtures according to the invention is determined in accordance with the Pfrengle (DIN ISO 4324 Tenside, Pulver und Granulate, Bestimmung des Schüttwinkels, December 1983, Beuth Verlag Berlin).

The flowability is determined by calculating the cone height or the ratio of the cone radius to the cone height of the powder or granules. The cone is created by pouring a specific amount of the substance to be studied from a confined device using a special funnel. The cone is poured until the product overflows a circular plate protruding from the base, creating a defined cone radius. The radius of the plate is determined. The funnel has an inner diameter of 10 mm. The plate has a radius of 50 mm. Five measurements are taken and averaged. The height is measured in millimeters using a measuring strip from the plate to the cone's apex. The ratio of the cone radius (50 mm) to the cone height is calculated from the average value.

For flame retardant mixtures according to the prior art, a bead cone height of 29.9 to 49.9 mm was determined at a spacing of 20 mm, and a radius to height ratio (=cotα) of 1.67 to 1.00 was determined at a spacing of 0.67.

The UL 94 fire rating (Underwriter Laboratories) was determined on specimens from each mixture at a thickness of 1.5 mm.

The following fire protection ratings are obtained according to UL 94:

V-0: The afterburning time does not exceed 10 seconds, the total afterburning time of 10 ignitions does not exceed 50 seconds, there is no burning dripping, the sample is not completely burned out, and there is no residual burning of the sample for more than 30 seconds after the end of ignition;

V-1: The afterburning time after ignition is not more than 30 seconds, the total afterburning time of 10 ignitions is not more than 250 seconds, and there is no residual flame of the sample for more than 60 seconds after the end of ignition. Other standards are the same as those of V-0;

V-2: Ignition of cotton wool by burning dripping, other standards are the same as V-1;

Not classifiable (nkl): Does not meet fire protection class V-2.

In the following examples, the heat resistance was determined on the flame retardant mixtures according to the invention and the processing window was determined on flame-retardant polymer molding materials.

Preparation, processing and testing of flame-retardant polymer molding materials and polymer moldings

The flame retardant component is mixed with the polymer pellets and any additives and added to PA 6,6 at a temperature of 230 to 260°C (glass-fiber-reinforced PBT) via a twin-screw extruder (Leistritz ZSE 27/44D) via a side feed at 260-310°C or to PA 6 at 250-275°C. The glass fibers are added via a second side feed. The homogenized polymer strands are removed, cooled in a water bath, and subsequently pelletized to form flame-retardant polymer molding materials.

After sufficient drying, the molding material is processed on an injection molding machine (Arburg 320C Allrounder) at a material temperature of 240-300° C. to give flame-retardant polymer moldings. These can be used as test pieces and tested and classified for flame retardancy according to the UL 94 test (Underwriter Laboratories).

The processing window of the PA GF30 compound was determined in an isothermal DSC experiment:

Flame-retardant polymer molding materials and flame-retardant polymer moldings were prepared according to the general specifications described above. The composition was 49.7% by weight of polyamide (Ultramid A27 E01 from BASF SE), 30% by weight of glass fiber (PPG glass fiber HP 3610EC10 from PPG), 12.6% by weight of the FSM (flame retardant) mixture according to the invention, 6.6% by weight of MPP (Melapur 200/70 from BASF), 0.8% by weight of zinc borate (Firebrake 500 from Rio Tinto Minerals), and 0.3% by weight of wax (Licowax E Gran from Clariant).

Since the lower limit of the processing window is not affected, the decomposition of the flame-retardant polymer molding material at the upper limit is determined as a measure of the processing window. For this purpose, the weight loss at a defined temperature is used.

The weight loss in % by weight was determined in air at 330° C. after a holding time of 60 minutes using DSC (differential thermal analysis).

Example 1 (comparison)

Diethylphosphinate without telomer and iron exhibits the heat resistance and processing windows listed in Table 2.

Examples 2 and 4

Aluminum diethylphosphinate without telomer was mixed with iron tris(diethylphosphinate) to form a physical mixture in a ploughshare mixer from the company by mixing for approximately 15 minutes until homogeneity was achieved. The flame retardant mixtures according to the invention contained 20 or 1000 ppm of iron.

The heat resistance and the processing window (both see Table 2) exceed those of pure aluminum diethylphosphinate (Table 2, comparative example 1).The heat resistance was determined for the flame retardant mixtures according to the invention and the processing window was determined for the flame-retardant polymer molding materials.

Examples 3 and 5

Aluminum diethylphosphinate without telomer was mixed with iron tris(dipropylphosphinate) to form a physical mixture in a ploughshare mixer by mixing for approximately 15 minutes until homogeneity was achieved. The flame retardant mixture according to the invention contained 50 or 13413 ppm of iron.

The heat resistance and the processing window (both see Table 2) exceed those of pure aluminum diethylphosphinate (Table 2, comparative example 1).The heat resistance was determined for the flame retardant mixtures according to the invention and the processing window was determined for the flame-retardant polymer molding materials.

Examples 6 to 17

Aluminum diethylphosphinate containing n-butylethylphosphinate, sec-butylethylphosphinate, or ethylhexylphosphinate in an ionically intercalated form was mixed with iron tris(diethylphosphinate) in a plowshare mixer for approximately 15 minutes until homogeneity was achieved. The amounts used are given in Table 3, and the composition of the flame retardant mixture according to the invention is given in Table 4. The heat resistance and processing window (both see Table 4) exceeded those of pure aluminum diethylphosphinate (Table 2, Comparative Example 1). The heat resistance of the flame retardant mixture according to the invention and the processing window of the flame-retardant polymer molding material were determined.

Examples 18 to 19

Aluminum diethylphosphinate containing n-butylethylphosphinate in an ion-intercalated form was mixed with iron tris(diethylphosphinate) in a plowshare mixer from the company for approximately 15 minutes until homogeneity was achieved. The amounts used are given in Table 3, and the composition of the flame retardant mixture according to the invention is given in Table 4.

The heat resistance and the processing window (both see Table 4) exceed those of pure aluminum diethylphosphinate (Table 2, comparative example 1).The heat resistance was determined for the flame retardant mixtures according to the invention and the processing window was determined for the flame-retardant polymer molding materials.

Examples 20 to 35

Aluminum diethylphosphinate containing n-butylethylphosphinate, sec-butylethylphosphinate or ethyl-n-hexylphosphinate in an ion-intercalated manner in the amounts specified in Tables 5 and 7 was mixed with an iron additive in a plowshare mixer of the company for approximately 15 minutes until homogeneity was achieved. The flame retardant mixtures according to the invention contained n-butylethylphosphinate, sec-butylethylphosphinate or ethyl-n-hexylphosphinate and iron in the amounts specified in Tables 6 and 8.

The heat resistance and the processing window (both see Tables 6 and 8) exceed those of pure aluminum diethylphosphinate (Table 2, Comparative Example 1).The heat resistance was determined for the flame retardant mixtures according to the invention and the processing window was determined for the flame-retardant polymer molding materials.

Examples 36 and 37

Aluminum diethylphosphinate containing n-butylethylphosphinate in coprecipitated form was mixed with iron tris(diethylphosphinate) in a plowshare mixer from the company for approximately 15 minutes until homogeneity was achieved. The amounts used are given in Table 7, and the composition of the flame retardant mixture according to the invention is given in Table 8.

The heat resistance and the processing window (both see Table 8) exceed those of pure aluminum diethylphosphinate (Table 2, comparative example 1).The heat resistance was determined for the flame retardant mixtures according to the invention and the processing window was determined for the flame-retardant polymer molding materials.

Example 38

Aluminum diethylphosphinate containing sec-butylethylphosphinate in an ionically intercalated manner was mixed first with aluminum n-butylethylphosphinate and then with iron tris(diethylphosphinate) in a plowshare mixer by mixing for about 15 minutes until homogeneity was achieved to form a physical mixture. The flame retardant mixture according to the invention contained 52 ppm of iron.

The heat resistance and the processing window (both see Table 8) exceed those of pure aluminum diethylphosphinate (Table 2, comparative example 1).The heat resistance was determined for the FSM mixtures according to the invention and the processing window was determined for the flame-retardant polymer molding materials.

In the above tables, the heat resistance was measured by means of thermogravimetry (TGA). The temperature given is the temperature at which there is a weight loss of 2% by weight.

The processing window of the polymer molding materials is likewise determined using TGA. In this case, the weight loss in wt. % is measured after 1 hour at 330° C. TGA is carried out under an air atmosphere.

In the case of polymer molding materials, these contain, to a large extent, the flame retardant composition according to the invention, polyamide, MPP polyphosphate melamine, glass fibers, zinc borate, and wax.

Claims (32)

1. A flame retardant mixture, comprising a) 0.0001 to 74.8% by weight of the dialkylphosphinate of formula (II) as component A) in, ^R1 and ^R2 may be the same or different and represent straight-chain, branched, or cyclic _C1 - _C18 -alkyl, _C6 - _C18 -aryl, _C7 - _C18 -arylalkyl, and/or _C7 - _C18 -alkylaryl. m represents 1 to 4, and M represents Mg, Ca, Al, Ti, Zn, Na and/or K; b) 0.0001 to 25% by weight of iron dialkylphosphinate (II), iron dialkylphosphinate (III), iron monoalkylphosphinate (II), iron monoalkylphosphinate (III), iron alkylphosphinate (II), iron alkylphosphinate (III), iron phosphite (II), iron phosphite (III), iron phosphate (II) and/or iron phosphate (III) as component B1); c) 0.1 to 40% by weight of the telomer of formula (III) as component C) H-(C _w H _2w ) _k P(O)(OM)(C _x H _2x ) _l -H (III) In equation (III), they are independent of each other. k represents 1 to 9, l represents 1 to 9, w represents 2 to 9, x represents 2 to 9, and M represents Mg, Ca, Al, Ti, Fe, Zn, Na, K and/or protonated nitrogen-containing bases. The groups ( _CwH2w ) _k and ( _CxH2x ) _l can be straight _- chain or _branched ; And/or the telomers are those of formula (I). in ^R3 and ^R4 may be the same or different and represent _C6 - _C10 -arylene, _C7 - _C20 -alkylarylene, _C7 - _C20 -arylalkylene and/or _C3 - _C16 -cycloalkyl or _C3 - _C16 -bicycloalkyl. M represents Mg, Ca, Al, Ti, Fe, Zn, Na, K and/or protonated nitrogen-containing bases; and d) 0.1 to 40% by weight as a synergist for component D); The sum of A), B1), C), and D) is 100% by weight, provided that A), B1), and C) are different compounds. 2. The flame retardant mixture according to claim 1, characterized in that, in formula (II), ^R1 and ^R2 are the same or different and independently represent methyl, ethyl, n-propyl, isopropyl, butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl (isopentyl), 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl (neopentyl), hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclopentylethyl, cyclohexyl, cyclohexylethyl, phenyl, phenylethyl, methylphenyl and/or methylphenylethyl. 3. The flame retardant mixture according to claim 2, characterized in that, in formula (II), ^R1 and ^R2 are the same or different and independently represent n-butyl and/or tert-butyl. 4. The flame retardant mixture according to claim 1 or 2, characterized in that component B1) comprises bis(diethylphosphino)ferric(II) and/or tri(diethylphosphino)ferric(III), bis(dipropylphosphino)ferric(II) and/or tri(dipropylphosphino)ferric(III), bis(butylethylphosphino)ferric(II) and/or tri(butylethylphosphino)ferric(III), bis(n-butylethylphosphino)ferric(II) and/or tri(n-butylethylphosphino)ferric(III), bis(sec-butylethylphosphino)ferric(II) and/or tri(sec-butylethylphosphino)ferric(III), bis(hexylethylphosphino)ferric(II) and/or tri ... tri(hexylethylphosphino)ferric(II) and/or tri(hexylethylphosphino)ferric(II) and tri(hexylethylphosphino)ferric(II) and tri(hexylethylphosphino)ferric(II) and tri(hexylethylphosphino)ferric(II) and tri(hexylethylphosphino)ferric(II) and tri(hexylethylphosphino)ferric( Iron(III) bis(dibutylphosphine) iron(II) and/or tri(dibutylphosphine) iron(III), bis(hexylbutylphosphine) iron(II) and/or tri(hexylbutylphosphine) iron(III), bis(octylethylphosphine) iron(II) and/or tri(octylethylphosphine) iron(III), bis(ethyl(cyclopentylethyl)phosphine) iron(II) and/or tri(ethyl(cyclopentylethyl)phosphine) iron(III), bis(butyl(cyclopentylethyl)phosphine) iron(II) and/or tri(ethyl(cyclohexylethyl)phosphine) iron(II) and/or tri(ethyl(cyclohexylethyl)phosphine) iron(II) and/or tri(ethyl(cyclohexylethyl)phosphine) iron(II) and/or tri(ethyl(cyclohexylethyl)phosphine) iron(II) and/or tri(ethyl(cyclohexylethyl)phosphine) iron(II) and/or tri(ethyl(cyclohexylethyl)phosphine) iron(III) 2,3-(cyclohexylethyl)phosphine iron (III), bis(butyl(cyclohexylethyl)phosphine iron (II) and/or tri(butyl(cyclohexylethyl)phosphine iron (III), bis(ethyl(phenylethyl)phosphine iron (II) and/or tri(ethyl(phenylethyl)phosphine iron (III), bis(butyl(phenylethyl)phosphine iron (II) and/or tri(butyl(phenylethyl)phosphine iron (III), bis(ethyl(4-methylphenylethyl)phosphine iron (II) and/or tri(ethyl(4-methylphenylethyl)phosphine iron (III), bis(butyl(4-methylphenylethyl)phosphine iron (II) and/or tri(butyl(4-methylphenylethyl)phosphine iron (II) and/or tri(butyl(4-methylphenylethyl)phosphine iron (III)) (4-Methylphenylethyl)phosphonic acid) iron (III), bis(butylcyclopentylphosphonic acid) iron (II) and/or tri(butylcyclopentylphosphonic acid) iron (III), bis(butylcyclohexylethylphosphonic acid) iron (II) and/or tri(butylcyclohexylethylphosphonic acid) iron (III), bis(butylphenylphosphonic acid) iron (II) and/or tri(butylphenylphosphonic acid) iron (III), bis(ethyl(4-methylphenyl)phosphonic acid) iron (II) and/or tri(ethyl(4-methylphenyl)phosphonic acid) iron (III), and/or bis(butyl(4-methylphenyl)phosphonic acid) iron (II) and/or tri(butyl(4-methylphenyl)phosphonic acid) iron (III); Iron (II) mono(ethylphosphonic acid) and/or iron (III) mono(ethylphosphonic acid), iron (II) mono(propylphosphonic acid) and/or iron (III) mono(propylphosphonic acid), iron (II) mono(butylphosphonic acid) and/or iron (III) mono(n-butylphosphonic acid), iron (II) mono(n-butylphosphonic acid), iron (II) mono(sec-butylphosphonic acid) and/or iron (III) mono(sec-butylphosphonic acid), iron (II) mono(hexylphosphonic acid) and/or iron (III) mono(hexylphosphonic acid), and/or iron (II) mono(octylphosphonic acid) and/or iron (III) mono(octylphosphonic acid); Ferric ethylphosphonate (II) and/or ferric ethylphosphonate (III), ferric propylphosphonate (II) and/or ferric propylphosphonate (III), ferric butylphosphonate (II) and/or ferric butylphosphonate (III), ferric n-butylphosphonate (II) and/or ferric n-butylphosphonate (III), ferric sec-butylphosphonate (II) and/or ferric sec-butylphosphonate (III), ferric hexylphosphonate (II) and/or ferric hexylphosphonate (III), and/or ferric octylphosphonate (II) and/or ferric octylphosphonate (III); The following iron (II) salts and/or iron (III) salts: ethyl (cyclopentylethyl) phosphonic acid, butyl (cyclopentylethyl) phosphonic acid, ethyl (cyclohexylethyl) phosphonic acid, butyl (cyclohexylethyl) phosphonic acid, ethyl (phenylethyl) phosphonic acid, butyl (phenylethyl) phosphonic acid, ethyl (4-methylphenylethyl) phosphonic acid, ethyl phenyl phosphonic acid, butyl (4-methylphenylethyl) phosphonic acid, butyl cyclopentyl phosphonic acid, butyl cyclohexylethyl phosphonic acid, butyl phenyl phosphonic acid, ethyl (4-methylphenyl) phosphonic acid, butyl (4-methylphenyl) phosphonic acid, ethyl oxyphosphonic acid and/or ethyl oxyphosphonobutyric acid, hydroxymethyl It exists in the form of ethyl-ethylphosphonic acid, 1-hydroxy-1-methylpropyl-ethylphosphonic acid, acylethylphosphonic anhydride, butyl-ethylphosphonic acid, butylethylphosphonic acid, ethyloxyphosphonoisobutyronitrile (1-cyano-1-methylethyl-ethylphosphonic acid), propylethylphosphonic acid, tert-butyl-ethylphosphonic acid, hydroxymethylbutyl-ethylphosphonic acid, 3-hydroxy-3-methylpentyl-ethylphosphonic acid, propoxyethyl-ethylphosphonic acid, phenylethyl-ethylphosphonic acid, 2-ethyloxyphosphonoethyl-lauric acid, ethylpentylphosphonic acid, tert-butoxyethyl-ethylphosphonic acid, hexylethylphosphonic acid and/or ethyloxyphosphonoethyl sulfate. 5. The flame retardant mixture according to claim 1 or 2, characterized in that, in formula (III), w and x each represent 2 or 3, k and l each represent 1 to 3, and M represents Al, Ti, Fe, or Zn. 6. The flame retardant mixture according to claim 1 or 2, characterized in that the telomer is a metal salt of the following substances: ethyl butyl phosphine, dibutyl phosphine, ethyl hexyl phosphine, butyl hexyl phosphine, ethyl octyl phosphine, sec-butyl ethyl phosphine, 1-ethyl butyl-butyl phosphine, ethyl-1-methylpentyl phosphine, di-sec-butyl phosphine (di-1-methylpropyl phosphine), propyl hexyl phosphine, dihexyl phosphine, hexyl-nonyl phosphine, propyl-nonyl phosphine, dinonyl phosphine, dipropyl phosphine, butyl-octyl phosphine, hexyl-octyl phosphine, dioctyl phosphine, ethyl (cyclopentylethyl) phosphine, butyl (cyclopentylethyl) phosphine, ethyl (cyclohexylethyl) phosphine, butyl (cyclohexylethyl) phosphine, ethyl (phenylethyl) phosphine, butyl (Phenylethyl)phosphonic acid, ethyl(4-methylphenylethyl)phosphonic acid, butyl(4-methylphenylethyl)phosphonic acid, butylcyclopentylphosphonic acid, butylcyclohexylethylphosphonic acid, butylphenylphosphonic acid, ethyl(4-methylphenyl)phosphonic acid and/or butyl(4-methylphenyl)phosphonic acid, ethyloxyphosphonoisobutyronitrile (1-cyano-1-methylethyl-ethylphosphonic acid), propylethylphosphonic acid, hydroxymethylbutyl-ethylphosphonic acid, 3-hydroxy-3-methylpentyl-ethylphosphonic acid, propoxyethyl-ethylphosphonic acid, phenylethyl-ethylphosphonic acid, ethylpentylphosphonic acid, tert-butoxyethyl-ethylphosphonic acid, ethyloxyphosphonoisohexanenitrile, hexylethylphosphonic acid and/or ethyloxyphosphonoethyl sulfate, wherein the metal of the metal salt is derived from Mg, Ca, Al, Ti, Fe, Zn, Na and/or K. 7. The flame retardant mixture according to claim 1 or 2, characterized in that the synergist is melamine phosphate, diazophosphate (melamine), pentaphosphate (melamine), triphosphate (melamine), tetraphosphate (melamine), hexaphosphate (melamine), diphosphate (melamine), tetraphosphate (melamine), pyrophosphate (melamine), polyphosphate (melamine), polyphosphate (melamine), and/or polyphosphate (melon); is a melamine condensation product; is a low polyester of tris(hydroxyethyl) isocyanurate/salt and aromatic polycarboxylic acids, benzoguanidine, tris(hydroxyethyl) isocyanurate/salt, allantoin, glycourea, melamine, cyanuric acid melamine, cyanuric acid urea, dicyandiamide and/or guanidine; is of the formula ( _NH4 ) _{yH3 -yPO4 or ( NH4PO3} ). The nitrogen-containing phosphate of _z , wherein y equals 1 to 3 and z equals 1 to 10,000; is aluminum phosphite, aluminum pyrophosphite, aluminum phosphonate, aluminum pyrophosphonate; is silicate, zeolite, silica, ceramic powder, zinc compound, tin oxide hydrate, magnesium hydroxide, hydrotalcite, magnesium carbonate and/or calcium magnesium carbonate. 8. The flame retardant mixture according to claim 7, wherein the melamine condensation product is melamine, melamine and/or melamine methyl ether. 9. The flame retardant mixture according to claim 7, wherein the zinc compound is zinc borate, zinc carbonate, zinc stannate, basic zinc stannate, zinc phosphate, zinc sulfide, zinc oxide, zinc hydroxide, basic zinc silicate, and/or zinc molybdate. 10. The flame retardant mixture according to claim 1 or 2, characterized in that components A) and B1) exist in the form of a physical mixture. 11. The flame retardant mixture according to claim 1 or 2, characterized in that components A), B1) and C) exist in the form of a physical mixture of each other. 12. The flame retardant mixture according to claim 1 or 2, characterized in that components A) and C) form a consistent compound with each other and exist in the form of a physical mixture with component B1). 13. The flame retardant mixture according to claim 1 or 2, characterized in that it has a particle size of 0.01 to 1000 μm, a bulk density of 50 to 1500 g/l, a compacted density of 100 g/l to 1100 g/l, an angle of packing of 5 to 45 degrees, a BET surface area of 1 to 40 ^m² /g, an L-color value of 85 to 99.9, an α-color value of -4 to +9, and a b-color value of -2 to +6. 14. The flame retardant mixture according to claim 1 or 2, characterized in that it has a particle size of 0.5 to 800 μm, a bulk density of 80 to 800 g/l, a compacted density of 600 g/l to 800 g/l, and an angle of packing of 10 to 40 degrees. 15. A method for preparing a flame retardant mixture according to any one of claims 1 to 14, characterized in that, a) In process stage 1, 0.9 to 1.1 molecules of olefin are added relative to each water-soluble salt or acid of hypophosphoric acid. b) In process stage 2, an additional 0.9 to 1.1 molecules of olefin are added to the dialkylphosphonic acid or its salt, based on each P from the intermediate in a). c) In process stage 3, 1 to 9 additional olefin molecules are added to 0 to 20% of the dialkylphosphinic acid molecules from process stage 1 to form a telomer, wherein, in the case of producing dialkylphosphinic acid, it is converted into the corresponding salt. d) In process stage 4, the intermediate products and metal salts from b) and/or c) are crystallized. e) In process stage 5, iron compound/elemental iron/iron alloy/component B1 is mixed in. 16. A method for preparing a flame retardant mixture according to any one of claims 1 to 14, characterized in that, a) In process stage 1, 0.9 to 1.1 molecules of olefin are added per unit phosphorus content, based on the amount of phosphorus on each water-soluble salt or acid of hypophosphite. b) In process stage 2, an additional 0.9 to 1.1 molecules of olefin are added to the dialkylphosphonic acid or its salt, based on each P from the intermediate in a). c) In process stage 3, 1 to 9 additional olefin molecules are added to 0.1 to 20% of the dialkylphosphinic acid molecules from process stage 1 to form a telomer, wherein, in the case of producing dialkylphosphinic acid, it is converted into the corresponding salt. d) In process stage 4, the intermediate product from c) and the metal salt are co-precipitated, and e) In process stage 5, iron compound/elemental iron/iron alloy/component B1 is mixed in. 17. A method for preparing a flame retardant mixture according to any one of claims 1 to 14, characterized in that, a) In process stage 1, 0.9 to 1.1 molecules of olefin are added per unit phosphorus content, based on the amount of phosphorus on each water-soluble salt or acid of hypophosphite. b) In process stage 2, an additional 0.9 to 1.1 molecules of olefin are added to the dialkylphosphonic acid or its salt, based on P on each intermediate from a), wherein, in the case of producing the dialkylphosphonic acid, it is converted into the corresponding salt. c) In process stage 3, the intermediate product from b) and the iron salt are co-precipitated, and d) In process stage 4, telomer/component C is mixed in. 18. A method for preparing a flame retardant mixture according to any one of claims 1 to 14, characterized in that, a) In process stage 1, 0.9 to 1.1 molecules of olefin are added per unit phosphorus content, based on the amount of phosphorus on each water-soluble salt or acid of hypophosphite. b) In process stage 2, an additional 0.9 to 1.1 molecules of olefin are added to the dialkylphosphonic acid or its salt, based on P on each intermediate from a), wherein, in the case of producing the dialkylphosphonic acid, it is converted into the corresponding salt. c) In process stage 3, the intermediate product and metal salt from b) are crystallized. d) In process stage 4, optionally incorporate telomers, and e) In process stage 5, iron compound/elemental iron/iron alloy/component B1 is mixed in. 19. The method according to any one of claims 15 to 18, characterized in that, as iron compounds, those having anions of Group 7; those having anions of oxyacids of Group 7; those having anions of Group 6; those having anions of oxyacids of Group 6; those having anions of Group 5; those having anions of oxyacids of Group 5; those having anions of oxyacids of Group 4; those having anions of oxyacids of Group 3; those having anions of pseudohalides; and those having anions of oxyacids of transition metals. 20. The method according to any one of claims 15 to 18, characterized in that, as an iron compound, it uses those having organic anions from: monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, and/or acidic hydroxyl functional groups, and/or as an alloy of iron with copper, tin, nickel, chromium, molybdenum, tungsten, or vanadium. 21. The method according to any one of claims 15 to 18, characterized in that, as the iron compound, those having organic anions from the following are used: acetic acid, trifluoroacetic acid, propionate, butyrate, valerate, caprylate, oleate, stearate, oxalic acid, tartaric acid, citric acid, benzoic acid, salicylate, lactic acid, acrylic acid, maleic acid, succinic acid, amino acids, p-phenolsulfonate, hydrated p-phenolsulfonate, hydrated acetylacetonate, tannic acid, dimethyl dithiocarbamate, trifluoromethanesulfonate, alkyl sulfonate and/or aralkyl sulfonate. 22. The method according to any one of claims 15 to 18, characterized in that, as the iron compound, the following are used: fluoride, chloride, bromide, iodide, iodate, perchlorate, oxide, hydroxide, peroxide, superoxide, sulfate, bisulfate, hydrated sulfate, sulfite, persulfate, nitrate, phosphide, nitrate, hydrated nitrate, nitrite, phosphate, superphosphate, phosphite, hypophosphite, pyrophosphate, carbonate, bicarbonate, basic carbonate, hydrated carbonate, silicate, hexafluorosilicate, hydrated hexafluorosilicate, stannate, borate, polyborate, perborate, thiocyanate. Iron compounds in the form of salts, cyanates, cyanides, chromates, chromites, molybdates, permanganates, formates, acetates, hydrated acetates, hydrated trifluoroacetates, propionates, butyrates, valerates, octanoates, oleates, stearates, oxalates, tartrates, citrates, basic citrates, hydrated citrates, benzoates, salicylates, lactates, hydrated lactates, acrylic acid, maleic acid, succinic acid, glycine, phenolates, p-phenol sulfonates, hydrated p-phenol sulfonates, hydrated acetylacetonate, tannins, dimethyl dithiocarbamates, trifluoromethanesulfonates, alkyl sulfonates, and/or aralkyl sulfonates. 23. The method according to any one of claims 15 to 18, characterized in that an initiator, inhibitor, free radical control agent, nucleating agent, co-crystallization agent, strong electrolyte, wetting agent, solvent, basic compound, flow aid, bleaching agent, coupling agent, adhesion enhancer and/or release agent are added during the process stage. 24. The method according to any one of claims 15 to 18, characterized in that acid, alkali, plastic additives and/or coating additives are added during the process stage. 25. The method according to any one of claims 15 to 18, characterized in that a free radical initiator, a photoinitiator, a strongly alkaline solution and/or a crystallization aid are added during the process stage. 26. The flame retardant mixture according to any one of claims 1 to 14 as an intermediate product for further synthesis, as a binder, as a crosslinking agent or accelerator in the curing of epoxy resins, polyurethanes and unsaturated polyester resins, as a polymer stabilizer, as a plant protectant, as a chelating agent, as a mineral oil additive, as a corrosion inhibitor, for use in detergents and cleaning agents and in electronic applications, as a flame retardant for wood and other cellulose-containing products, as a reactive and/or non-reactive flame retardant for polymers, and/or for use in the preparation of flame-retardant polymer molding materials. 27. The flame retardant mixture according to any one of claims 1 to 14 as a flame retardant for varnishes and foamed coatings, or for use in imparting flame retardancy to polyester and pure and blended cellulose fabrics by impregnation. 28. Use of the flame retardant mixture according to any one of claims 1 to 14 as a flame retardant and/or for the preparation of flame retardant polymer molded articles. 29. Flame-retardant thermoplastic or thermosetting polymer molding materials, polymer films, polymer filaments, and polymer fibers, comprising 0.5 to 50% by weight of a mixture of flame retardants according to any one of claims 1 to 14, 0.5 to 95% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55% by weight of an additive, and 0 to 70% by weight of a filler or reinforcing material, wherein the sum of said components is 100% by weight, and wherein said polymer is a thermoplastic polymer of the type of HI (high impact) polystyrene, polyphenylene ether, polyamide, polyester, polycarbonate type, and ABS (acrylonitrile-butadiene-styrene) or PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) or PPE/HIPS (polyphenylene ether/HI polystyrene) plastic blend, or a thermosetting polymer of the type of formaldehyde-phenol resin polymer, epoxide-phenol resin polymer, melamine-phenol resin polymer, unsaturated polyester, epoxy resin, or polyurethane. 30. The thermoplastic or thermosetting polymer molding material, polymer film, polymer filament and polymer fiber according to claim 29, characterized in that it contains other additives, wherein the other additives are antioxidants, UV stabilizers, γ-ray stabilizers, hydrolytic stabilizers, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact modifiers, dyes or pigments. 31. A flame-retardant thermoplastic or thermosetting polymer molded article comprising 0.5 to 50% by weight of a flame retardant mixture according to any one of claims 1 to 14, 0.5 to 95% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, 0 to 55% by weight of an additive, and 0 to 70% by weight of a filler or reinforcing material, wherein the sum of said components is 100% by weight, and said polymer is a thermoplastic polymer of the type of HI (high impact) polystyrene, polyphenylene ether, polyamide, polyester, polycarbonate type and ABS (acrylonitrile-butadiene-styrene) or PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) or PPE/HIPS (polyphenylene ether/HI polystyrene) plastic blend, and/or a formaldehyde-phenol resin polymer, an epoxide-phenol resin polymer, a melamine-phenol resin polymer, an unsaturated polyester, an epoxy resin and/or a polyurethane type thermosetting polymer. 32. The thermoplastic or thermosetting polymer molded article according to claim 31, characterized in that it comprises other additives, wherein the other additives are antioxidants, UV stabilizers, γ-ray stabilizers, hydrolytic stabilizers, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact modifiers, dyes or pigments.