EP3099760A1

EP3099760A1 - Halogen-free solid flame retardant mixture and use thereof

Info

Publication number: EP3099760A1
Application number: EP15701669.2A
Authority: EP
Inventors: Harald Bauer; Sebastian HÖROLD; Martin Sicken
Original assignee: Clariant International Ltd
Current assignee: Clariant International Ltd
Priority date: 2014-01-29
Filing date: 2015-01-19
Publication date: 2016-12-07
Also published as: KR102405986B1; JP6630278B2; CN109824939A; EP3505596A1; CN109796628A; US20160340588A1; PL3505596T3; DE102014001222A1; EP3521402B1; KR20160114160A; EP3505597A1; US10508238B2; WO2015113740A1; EP3505597B1; EP3505599A1; JP2017508832A; EP3505598A1; EP3521402A1; CN109810291A; EP3505596B1

Abstract

The invention relates to a halogen-free flame retardant mixture containing between 1 - 99 wt.% of a component A and between 1 - 99 wt.% of a component B. Component A comprises between 85 - 99.995wt.-% of a solid diethylphosphinic acid salt of the metals Mg, Ca, AI, Sb, SN, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and/or a protonated nitrogen base and between 0.005 - 15 wt.-% of non-combustible additives and component B is in the form of an aluminum phosphite.

Description

Halogen-free solid flame retardant mixture and its use.

Flame retardant mixtures of various types are used for the flame-retardant finishing of polymers. It is necessary that in the typical process for polymer production, the components to be added, including the flame retardants, have good flowability and flowability in order to be distributed evenly in the polymer, so that its properties are not adversely affected. The fluidity is influenced by grain properties such. B. grain size, particle size distribution, surface texture of the grains, water content or moisture and different particle shapes. Depending on the particle size or frequency of the particles of different sizes, they roll off each other differently. Round particles with a uniform surface should flow more easily than those with an irregular shape. Depending on the chemical surface, humidity or

electrostatic properties, the flow properties differ.

If powders are processed with poor flow properties, often an irregular dosage and thus an uneven composition and distribution in the polymer, so that from one molding to molding

insufficient flame retardancy results.

According to the prior art, the flowability can be increased by admixtures of release agents and foreign bodies. Klein describes as a solution to this problem in soap-oils-fats waxes 94 (1968), 849 the addition of

Calcium stearate and Aerosil in amounts of 5,000 to 10,000 ppm. The silicate-containing auxiliaries proposed here for improving the flowability are extremely finely divided. You can be inhaled and are suspected

Cause lung diseases.

WO 2003 / 035736A1 describes Melamincyanurataggregate by

Binders are held together. The task there is in the

Improvement of the uniform distribution of the aggregates by an improvement of the Flowability. This term is also referred to as fluidity of bulk materials (powder, agglomerates, granules, etc.). Here, with the addition of 1,000 ppm to 10 wt .-% organic excipient, the corresponding particles of a specific size are glued to larger aggregates and thus increases the flowability. These organic auxiliaries are typically organic

Compounds, for example polymers or copolymers based on

Vinyl pyrrolidone, vinyl acetate and vinyl caprolactam, epoxies, urethanes,

Acrylates, esters, amides, stearates, olefins, cellulose derivatives or

Mixtures thereof. The aforementioned aggregates can u. a. be prepared by dispersing the particles in advance in an aqueous slurry and adding a water-soluble auxiliary.

EP-1522551 A1 describes phosphorus-containing flame retardant agglomerates of low bulk density, the aggregates and / or primary particles

Contain phosphinic salts and / or Diphosphinsäuresalzen and / or their polymers and stick together using an adjuvant. These agglomerates are accessible by spray granulation. .

To make the flame retardant agglomerates as homogeneous as possible in one

To distribute polymer a particularly good flow behavior of the bulk material is sought. This is achieved by the use of the aforementioned

Flammschutzmittelagglomerats with low bulk density and still low dust. Low tendency to dust is important, since dusting may cause the dosage to be uneven when incorporated into polymers in extruders, resulting in an inhomogeneous distribution of the flame retardant in the extruder

Polymer yield. This, in turn, may be due to consequent local

Under dosing be detrimental to the flame retardancy.

The EP-1522551 A1 is concerned only with the increase of the flowability or flowability, but not with the improvement of the uniformity of

Flowability. JP-2003138264A1 and JP-2003138265A1 describe a good flowability for halogen-containing flame retardants by using particularly large particles (0.8 to 2 mm). In JP-2005171206A1 Flammschutzmittelmischungen with good

Flowability obtained by combining finely divided basic metal oxide with platelet-shaped, finely divided, fibrous finely divided or amorphous finely divided inorganic particles and inorganic flame retardants.

WO-2010075087A1 describes a free-flowing

Flame retardant composition is absorbed from a liquid phosphorus-containing flame retardant in the latter on a support. Flame-retardant polymer molding compounds are u. a. For example, prepared in which the flame retardant components on the side feeder of a

Twin-screw extruder at temperatures of 250 to 310 ° C in one

Polymer melt are incorporated. Glass fibers are added - if necessary - via a second side feed. The resulting homogenized polymer strand is stripped off, cooled in a water bath and then granulated.

In case of uneven flowability of the flame retardant components, it can lead to overfilling of filling funnels or underdoses in time

inadequate product supply from the storage bunkers. Both are undesirable production disturbances. As a result, chemicals can leak into the operating environment. It can also be unsteady

Product compositions come in the flame-retardant polymer molding compositions. In case of underdosing, this means insufficient

Flame retardant for the polymer molding compound. The present invention is therefore based on the object to provide a flame retardant mixture with uniform flowability available. Another object of the present invention is the prevention of process disturbances in the manufacture of flame retardant

Polymer molding compositions.

The flame retardant mixtures according to the invention contain no

Binders leading to a higher adhesion of the powder particles

Lead aggregates. The binders would only affect the effectiveness of

Reduce flame retardants by reducing the amount of active substance (that is the flame retardant) by means of flammable auxiliaries. It is a further object of the invention to dispense with the use of water-soluble organic adjuvants to improve the flowability, as well as the grain size of the flame retardant particles should not be increased.

Surprisingly, it has been found that the halogen-free flame retardant mixtures according to the invention have a uniform flowability and at the same time achieve a good flameproofing effect.

The invention therefore relates to a halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% of a component B, wherein component A 85 to 99.995 wt .-% of a solid

Diethylphosphinic acid salt of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base and 0.005 to 15% by weight contains non-combustible additives and component B is aluminum phosphite.

The halogen-free flame retardant mixture particularly preferably contains from 20 to 80% by weight of component A and from 20 to 80% by weight of component B. Preferably, the component A contains the halogen-free

Flame retardant mixture 92 to 99.9 wt .-% solid

Aluminiumdiethylphosphinsäuresalz and 0.5 to 8 wt .-% non-combustible additives.

The additives are preferably dialkylphosphinic salts of the formula (IV)

wherein R ¹ and R ^{2 are the} same or different and are independently ethyl, butyl, hexyl and / or octyl and M is Mg, Ca, Al, Sb, SN, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr , Mn, Li, Na, K and / or a protonated nitrogen base means with the proviso that R ¹ and R ^{2 are} not simultaneously ethyl; and / or that the additives are sulfates, phosphates, phosphonates, nitrates, chlorides, sulfites and / or acetates, and the sulfates, phosphates, phosphonates, nitrates, chlorides, sulfites and / or acetates are compounds with cations the alkali metals, the alkaline earth metals, the third main group, the subgroups of the Periodic Table and / or protonated nitrogen bases.

The dialkylphosphinic acid salts of the formula (IV) are preferably ethyl-butylphosphinic acid salts, butyl-butylphosphinic acid salts, ethyl-hexylphosphinic acid salts, butyl-hexylphosphinic acid salts and / or hexyl-hexylphosphinic acid salts.

The cations are preferably those of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na and / or K. The protonated nitrogen bases are preferably ammonia, primary, secondary, tertiary and / or quaternary amines.

Preferably, the sulfates are sodium sulfates,

Sodium aluminum sulphates, alunites, aluminum sulphates, calcium sulphate, cerium sulphates, iron sulphates, potassium hydrogen sulphates, potassium sulphate, magnesium sulphates,

Manganese sulfates, monolithium sulfate, titanium sulfates, zinc sulfate, tin sulfates,

Zirconium sulfates and / or their hydrates. The phosphates are preferably aluminum phosphates,

Aluminum hydrogenphosphates, aluminum chloride phosphate,

Calcium hydrogen phosphates, calcium magnesium phosphates,

Calcium chloride phosphates, calcium aluminum phosphate, calcium carbonate phosphate, calcium phosphates, cerium phosphates, ceric acid phosphate, lithium phosphate, lithium hydrogen phosphate, magnesium phosphates,

Magnesium hydrogenphosphates, potassium phosphates, potassium aluminum phosphate, potassium hydrogenphosphates, sodium hydrogenphosphates, sodium hydrate phosphates, sodium aluminum phosphates and / or their hydrates. The phosphonates are preferably mono- (Cn ₈ -alkyl) -

Phosphonates, mono (C ₆ -C 10 -aryl) phosphonates and / or mono- (C _1-8 -aralkyl) -phosphonates.

Preferably, the nitrates are aluminum nitrate, calcium nitrate, cerium nitrate, iron nitrates, potassium nitrate, lithium nitrate, magnesium nitrate,

Manganese nitrates, sodium nitrate, titanium nitrates, zinc nitrate, tin nitrates and / or

Zirconium nitrates and / or their hydrates.

The acetates are preferably aluminum acetate, calcium acetate, cerium acetate, iron acetate, lithium acetate, potassium acetate, sodium acetate,

Magnesium acetate, manganese acetate, titanium acetate, zinc acetate, tin acetate,

Zirconium acetate, aluminum chloride acetate, aluminum hydrogen chloride acetate and / or their hydrates. Preferably, the sulfites are potassium sulfites,

Potassium hydrogen sulfites, potassium metabisulfite, sodium sulfites, sodium metabisulfite, sodium hydrogen sulfites, ammonium sulfites and / or their hydrates.

Preferably, the chlorides are aluminum chloride,

Calcium acetate chloride, calcium chloride, iron chloride, iron magnesium chloride, iron manganese chloride, iron chloride, lithium chloride, magnesium chloride, titanium chloride, titanium oxide chloride, zinc chloride, zinc aluminum chloride, zinc oxide chloride, tin chloride, zirconyl chloride, aluminum chloride hydroxide, calcium chloride chloride, iron hydroxide chloride, lithium hydroxide chloride, magnesium hydroxide chloride,

Magnesium chloride hydroxide, zinc chloride hydroxide, stannous chloride,

Manganese chloride, potassium chloride, potassium aluminum chloride and / or their hydrates. Preferably, the aluminum phosphites are those of

Formulas (I), (II) and / or (III)

Al ₂ (HPO ₃ ) ₃ x (H ₂ O) _q (I) in the

q 0 to 4

means

Al ₂ , ooM ₂ (HPO ₃ ) y (OH) _v x (H ₂ O) _w (II) in the

M alkali metal ions

z 0.01 to 1.5

y is 2.63 to 3.5

v 0 to 2 and

w 0 to 4

means Al2, oo (HPO ₃₎ u (H ₂ PO ₃₎ tx (H ₂ 0) _s (III) in the

u 2 to 2.99

t 2 to 0.01 and

s 0 to 4

means, and / or mixtures of aluminum phosphite of the formula (I) with

sparingly soluble aluminum salts and nitrogen-free foreign ions

Mixtures of aluminum phosphite of formula (III) with aluminum salts to give aluminum phosphite [Al (H2P0 ₃ ) ₃ ], aluminum secondary phosphite [Al ₂ (HPO ₃ ) ₃ ], basic aluminum phosphite [Al (OH) (H ₂ PO ₃ ) ₂ * 2aq] to

Aluminum phosphite tetrahydrate [Al ₂ (HPO ₃ ) ₃ ^* 4aq] to give aluminum phosphonate, Al ₇ (HPO ₃ ) ₉ (OH) ₆ (1,6-hexanediamine) ₁ , 5 * 12H ₂ O, Al ₂ (HPO ₃ ) ₃ ^* xAl ₂ O ₃ ^* nH ₂ O with x = 2.27-1, around Al ₄ H ₆ Pi ₆ 0i ₈ and / or around mixtures of 0-99.9% by weight

Al ₂ (HPO ₃ ) ₃ ^* nH ₂ O with 0.1-100% by weight of sodium aluminum phosphite.

The aluminum phosphite is preferably a mixture of 50-99% by weight Al ₂ (HPO ₃ ) ₃ × (H ₂ O) _q in which q is 0 to 4 and 1 to 50% by weight sodium aluminum phosphite.

The aluminum phosphite is preferably also a mixture of 50-99% by weight Al ₂ (HPO ₃ ) ₃ × (H ₂ O) _q in which q is 0 to 4 and 1-50% by weight Al ₂ , ooM _z (HPO ₃ ) y (OH) _v x (H ₂ O) _w (II) in the M sodium, z 0.005 to 0.15, y 2.8 to 3, 1, v 0 to 0.4 and w is 0 to 4.

Preferably, in the halogen-free flame retardant mixture

Component A has a mean particle size d50 of 0.05 to 10μιη and the

Component B has a mean particle size d50 of 0.05 to 10 pm and a residual moisture content of 0.05 to 8 wt .-%. The invention also relates to a process for the preparation of a halogen-free flame retardant mixture according to one or more of claims 1 to 17, characterized in that the components A and B are mixed together in powder form and optionally sieved.

The invention further relates to a process for the preparation of the halogen-free flame retardant mixture, characterized in that one

Diethylphosphinsäuresalz the metals Mg, Ca, Al, Sb, SN, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base with non-combustible additives and the component Mix B in powder form.

The invention also relates to the use of a halogen-free

Flame retardant mixture according to one or more of claims 1 to 13 as an intermediate for further syntheses, as a binder, as a crosslinker or

Accelerator in the curing of epoxy resins, polyurethanes, unsaturated polyester resins, as polymer stabilizers, as plant protection products, as

Sequestering agent, as a mineral oil additive, as a corrosion inhibitor, in detergent and cleaner applications, in electronic applications. Preference is given to the use of a halogen-free flame retardant mixture according to one or more of claims 1 to 13 in or as flame retardants, as flame retardants for clearcoats and intumescent coatings, in or as flame retardants for wood and other cellulose-containing products, in or as reactive and / or non-reactive flame retardants for Polymers, for the preparation of flame-retardant polymer molding compositions, for the production of

flame-retardant polymer moldings and / or for the flame-retardant finishing of polyester and cellulose pure and mixed fabrics by impregnation and / or as a synergist and / or synergist in other flame retardant mixtures.

The invention also relates to flame-retardant thermoplastic or thermosetting polymer molding compounds, polymer moldings, films, filaments and / or fibers, containing 0.1 to 45 wt .-% halogen-free flame retardant mixture according to one or more of claims 1 to 13, 55 to 99.9 wt .-%

thermoplastic or thermosetting polymer or mixtures thereof, 0 to 55 wt .-% of additives and 0 to 55 wt .-% filler or

Reinforcement materials, wherein the sum of the components is 100 wt .-%.

Preference is given to flame-retardant thermoplastic or thermosetting polymer molding compositions, polymer moldings, films, filaments and / or fibers, containing 1 to 30 wt .-% halogen-free flame retardant mixture according to one or more of claims 1 to 13, 10 to 97 parts by weight. % thermoplastic or thermosetting polymer or mixtures thereof, 1 to 30 wt .-% additives and 1 to 30 wt .-% filler or reinforcing materials, wherein the sum of the components is 100 wt .-%. The invention further relates to flame-retardant thermoplastic or

Thermosetting polymer molding compounds, polymer moldings, films, filaments and / or fibers, comprising a halogen-free flame retardant mixture according to one or more of claims 1 to 13, characterized in that the polymer is thermoplastic polymers of the type polystyrene HI ( High-impact), polyphenylene ethers, polyamides, polyesters, polycarbonates and blends or polymer blends of the ABS (acrylonitrile-butadiene-styrene) or PC / ABS (polycarbonate / acrylonitrile-butadiene-styrene) or PPE / HIPS type

(Polyphenylene ether / polystyrene Hl) plastics and / or thermosetting

Polymers of the type unsaturated polyester or epoxy resins is.

Most preferably, the polymer is polyamide 4/6

(Poly (tetramethylene adipamide), poly (tetramethylene adipamide) to polyamide 6 (polycaprolactam, poly-6-aminohexanoic acid) to polyamide 6/6

((Poly (N, N'-hexamethylene adipamide) and / or HTN (high temperature nylon).

Component A preferably contains 99.1 to 99.95% by weight of solid aluminum diethylphosphinate and 0.05 to 0.9% by weight of non-combustible additives. Hereinafter, the term diethylphosphinic acid salt always includes a diethylphosphinic salt of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base.

In one embodiment of the invention, the particularly preferred additives are dialkylphosphinic acid telomers, such as, for example, B. ethyl-butylphosphinic acid salts, butyl-butylphosphinic acid salts, ethyl hexylphosphinic acid salts, butyl-hexylphosphinic acid salts, hexyl hexylphosphinic acid salts and other metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe , Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base.

Preferred here is a halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% of a component B, wherein component A 85 to 99.995 wt .-% of a Diethylphosphinsäuresalzes the above metals and 0.005 to 15 wt % non-combustible additives and component B is aluminum phosphite.

Also preferred is a halogen-free flame retardant mixture containing 10 to 90 wt .-% of a component A and 10 to 90 wt .-% of a component B, wherein component A 85 to 99.995 wt .-% of a Diethylphosphinsäuresalzes the above metals and 0.005 to 15 wt % non-combustible additives and component B is aluminum phosphite. Also preferred is a halogen-free flame retardant mixture containing 20 to 80 wt .-% of a component A and 20 to 80 wt .-% of a component B, wherein component A 85 to 99.995 wt .-% of a Diethylphosphinsäuresalzes of the aforementioned metals and 0.005 to 15 wt % non-combustible additives and component B is aluminum phosphite.

Particularly preferred is a halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% of a component B, wherein component A 92 to 99.9 wt .-% of a Diethylphosphinsäuresalzes of the aforementioned metals and 0.1 to 8 wt .-% non-combustible additives and it is in the component B to

Aluminum phosphite acts. Particularly preferred non-combustible additives are dialkylphosphinic acid

Telomeres in their form as salts such. B. ethyl-butylphosphinic acid salts, butyl-butylphosphinic acid salts, ethyl-hexylphosphinic acid salts, butyl-hexylphosphinic acid salts, hexyl-hexylphosphinic acid salts of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr , Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base.

Preferred halogen-free flame retardant mixtures according to the invention which contain dialkylphosphinic acid telomers as non-combustible additive: I) Halogen-free flame retardant mixture comprising 1 to 99% by weight of component A and 1 to 99% by weight of aluminum phosphite, component A being from 85 to 99.995% by weight .-% Diethylphosphinsäuresalz and 0.005 to 15 wt .-% dialkylphosphinic telomers contains. II) Halogen-free flame retardant mixture containing 10 to 90 wt .-% of a component A and 10 to 90 wt .-% aluminum phosphite, wherein

Component A contains from 85 to 99.995% by weight of diethylphosphinic acid salt and from 0.005 to 5% by weight of dialkylphosphinic acid telomers. III) Halogen-free flame retardant mixture containing 20 to 80 wt .-% of a component A and 20 to 80 wt .-% aluminum phosphite, wherein

Component A contains from 85 to 99.995% by weight of diethylphosphinic acid salt and from 0.005 to 15% by weight of dialkylphosphinic telomers. IV) Halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% aluminum phosphite, wherein

Component A 92 to 99.9 wt .-% Diethylphosphinsäuresalz and 0.1 to

Contains 8 wt .-% dialkylphosphinic telomers. The non-combustible additives may preferably also be sulfates. Preferred sulfates are then those with cations of the alkali metals and with cations of protonated nitrogen bases z. B. of ammonia, primary, secondary, tertiary and quaternary amines and with cations of

alkaline earth metals; with cations of the elements of the third main group; with cations of the subgroup elements. Particularly preferred subgroup elements are titanium, iron, zinc and mixtures thereof.

Preferred sulfates are those with cations of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base. Particularly preferred sulfates are sodium sulfate, sodium aluminum sulfate and alunite.

Further preferred sulfates are:

Aluminum sulfate, calcium sulfate, cerium (II) sulfate, cerium (IV) sulfate, cerium sulfate,

Iron (II) sulfate, iron (III) sulfate, iron sulfate, potassium sulfate, potassium hydrogen sulfate, magnesium sulfate, magnesium sulfate, manganese (II) sulfate, manganese (III) sulfate,

Manganese (IV) sulfate, manganese sulfate, monolithium sulfate, sodium sulfate, sodium sulfate, titanium (II) sulfate, titanium (III) sulfate, titanium (IV) sulfate, titanium sulfate, zinc sulfate, tin (II) sulfate, tin (III) sulfate, tin ( IV) sulfate, tin sulfate, zirconium (II) sulfate, zirconium (IV) sulfate, zirconium sulfate.

Preferred alunites are:

Aluminite (AI ₂ (OH) ₄ (S0 ₄₎ 7H ₂ O), Metabasaluminite (Al ₄ (OH) ₀ (SO _4)),

Metaaluminite (AI ₂ (OH) ₄ (S0 ₄₎ 5H ₂ O), Rostite (AI (OH) (S0 ₄₎ 5H ₂ 0), Zaherite (Ali ₂ O ₁₃ (SO ₄₎ ₅ · xH ₂ 0), Aluminumhydroxidoxidsulfat ( Al ₃ o (OH) ₅₆ O ₈ (SO ₄ ) 9),

Aluminum hydroxide oxide sulphate hydrate, aluminum hydroxide sulphate (Al (OH) _{2 24} (SO ₄ ) o.38), aluminum hydroxide sulphate hydrate, aluminum hydroxide sulphate (Al ₃ (OH) ₅ (SO) ₂ ), aluminum hydroxide oxide sulphonate nonahydrate, aluminum hydroxide sulphate (Al ₄ (OH) i ₀ (SO ₄ )), Aluminum hydroxide oxide sulphate hydrate, Rostite (Al (OH) (S0 ₄ ) 5H ₂ O), aluminum hydroxide sulphate (Al ₇ (OH) i ₇ (S0 ₄ ) 2),

Aluminum hydroxide sulphate dodecahydrate, paraluminite (Al ₄ (OH) ₁₀ (SO ₄ ) 10H ₂ O), metaaluminite (Al ₂ (OH) ₄ (SO ₄ ) 5H ₂ O), rock arabinite (Al ₄ (OH) ₁₀ (SO ₄ ) 5H ₂ O), aluminates (Al ₂ (OH) ₄ (S0 ₄ ) 7H ₂ O), aluminum hydroxide sulfate (Al ₃ (OH) ₇ (SO ₄ )), aluminum hydroxide sulphate hydrates, aluminum hydroxide sulphate (Al ₃ (OH) ₅ (SO ₄ ) ₂ ) Aluminum hydroxide sulphate dihydrate, aluminum hydroxide sulphate (Al (OH) ₂ 7 (S0) o.is), aluminum hydroxide sulphate hydrate, aluminum hydroxide sulphate (Al ₇ (OH) ₁₇ (SO ₄ ) ₂ ), aluminum hydroxide sulphate hydrate, aluminum hydroxide sulphate (Al (OH) (SO)),

Aluminum hydroxide sulphate hydrate, aluminum hydroxide sulphate (Al (OH) i ₀ (SO ₄ )), aluminum hydroxide sulphate decahydrate, jurbanite (Al (OH) (SO ₄ ) 5H ₂ O),

Aluminum hydroxide sulfate (Al ₄ (OH) ₁₀ (SO ₄ )), aluminum hydroxide sulfate pentahydrate, aluminum hydroxide sulfate (Al ₆ (OH) i ₆ (SO ₄ )), aluminum hydroxide sulfate hydrate, basaluminite (Al ₄ (OH) ₁₀ (SO ₄ ) 5H ₂ O), aluminum hydroxide sulfate (Al (OH) (SO ₄ )), aluminum hydroxide sulfate pentahydrate, minamiit (Na, Ca) i _-x Al ₃ (SO) ₂ (OH) 6, aluminum sulfate hydrate oxide Al ₆ 05 (SO ₄ ) ₄ * xH ₂ O, zaherite-16A Al ₂ (SO ₄ ) 5 (OH) ₂₆ , aluminum sulphate hydroxide Al ₄ SO ₄ (OH) ₁₀ , zaherite-18A Al ₁₂ (SO ₄ ) ₅ (OH) ₂₆ * 20H ₂ O, hydrobasaluminite with Al ₄ SO (OH) i ₀ * 36H ₂ O, aluminum sulphate hydroxide hydrate

Al ₃ (S0 ₄ ) ₂ (OH) ₅ * 9H ₂ 0, basaluminite / rock banyanite Al ₄ SO ₄ (OH) ₁₀ * 4H ₂ O, aluminite Al ₂ (SO ₄ ) (OH) ₄ * 7H ₂ O, syn Winebergit AI ₄ SO ₄ (OH) ₁₀ * 7H ₂ O, Felsobanyait AI ₄ SO ₄ (OH) i ₀ * 5H ₂ O, syn-Metaaluminit AI ₄ S0 ₄ (OH) ₄ * 5H ₂ O, Rostit

AI ₄ SO ₄ (OH) * 5H ₂ O, Al ₂ 0 3 Aluminiumsulfathydroxidhydrat ₃ * 4 S0 ₃ * H ₂ O, natroalunite NaAl ₃ (SO ₄₎ ₂ (OH). ₆ Preferred halogen-free flame retardant mixtures according to the invention which contain sulfate as non-combustible additive:

I) Halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% aluminum phosphite, wherein

Component A 95 to 99.995 wt .-% Diethylphosphinsäuresalz and 0.005 to 5 wt .-% sulfate. II) Halogen-free flame retardant mixture containing 10 to 90 wt .-% of a component A and 10 to 90 wt .-% aluminum phosphite, wherein

Component A 95 to 99.995 wt .-% Diethylphosphinsäuresalz and 0.005 to 5 wt .-% sulfate.

III) Halogen-free flame retardant mixture containing 20 to 80 wt .-% of a component A and 20 to 80 wt .-% aluminum phosphite, wherein

IV) Halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% aluminum phosphite, wherein

Component A 99.1 to 99.99 wt .-% Diethylphosphinsäuresalz and 0.01 to 0.9 wt .-% sulfate.

The non-combustible additives may preferably also be phosphates.

Preferred phosphates are those with cations of the alkali metals and with cations of protonated nitrogen bases z. B. of ammonia, primary, secondary, tertiary and quaternary amines and with cations of

Preferred phosphates are those with cations of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated one

Nitrogen base. Preferred phosphates are aluminum phosphate AlPO _4, Al ₂ 0 ₃ ^* P ₂ O5, AI ₃₆ P36Oi _44, AL ₁₆ Pi ₆ 0 ₆₄ AI ₈ P ₈ O _22, Al ₂ O ₃ ^* x P ₂ 0 _5, Al ₂ O ₃ ^* 0.95P ₂ O ₅ , Al ₂ O ₃ ^* 0.86P ₂ O ₅ , Al ₁₂ P ₁₂ O ₄₈ , Al ₂ P ₆ 0i8, Aluminum _{phosphate hydrate} Al ₂ P _{1 I94} O ₇ , ₈₅ ^* 2H ₂ O, AIPO ₄ ^* xH ₂ O, AIPO4 ^* 0.45H ₂ O, Al ₃₂ P ₃₂ O ₁₂₈ ^* xH ₂ O, Al ₆ P ₆ O ₂₄ ^* 4H ₂ O, AIPO ₄ ^* 1, 67H ₂ O, Al ₄ (P ₂ O ₇ ) ₃ ^* 12H ₂ O,

Al ₂ P ₂ O ₈ ^* 3H ₂ O, AIP ₆ O ₁₈ ^* 9.5H ₂ O, Al ₆ P ₆ O ₂₁ ^* 8H ₂ O,

Aluminum hydrogen phosphate AI (H ₂ PO ₄ ) ₃ , H ₂ (AIPOPO ₄ ) 3,

Aluminum hydrogen phosphate hydrate AIH ₆ (PO ₄ ) ₃ ^* 2H ₂ O, AlH ₃ (PO ₄ ) ₂ ^* nH ₂ O,

Al (HP ₂ 0 ₇ ) ^* 2.5H ₂ O, AlH ₃ (PO ₄ ) ₂ ^* 3H ₂ O,

Aluminum chloride phosphate AI (PO ₂ Cl ₂ ) ₃ ,

Calcium hydrogen phosphate Ca ₃ H ₂ P ₄ O ₄ , Ca (H ₂ PO) _2, CaH ₂ PO ₇ , Ca ₄ H ₂ (P ₃ O ₁ O) ₂ , CaPO ₃ (OH),

Calcium magnesium phosphate Ca ₃ Mg ₃ (P0 ₄ ) ₂ , Ca ₇ Mg ₂ P ₆ 0 ₂₄ , CaMgP ₂ O ₇ ,

(Ca, Mg) ₃ (PO ₄ ) ₂ , calcium chloride phosphate Ca ₂ PO ₄ Cl,

Calcium phosphatate Ca ₃ P ₂ O ₇ , CaP ₄ On, Ca ₂ P ₆ O ₁₇ , Ca ₃ (P ₅ O ₁₄ ) ₂ , CaP ₂ O ₆ , CaP ₂ 0 ₇ , Ca ₄ P ₆ O ₁₉ , Ca ₄ (P0 ₄ ) ₂ , Ca _{x + 2} P _2x 0 _{6x + 2} ,

Calcium aluminum phosphate Ca ₉ Al (PO) ₇ ,

Calcium carbonate phosphate Cai ₀ (PO) ₆ CO ₃ ,

Calcium phosphate hydrate Ca ₂ P ₂ O ₇ * 2H ₂ O, beta-Ca ₂ (P ₄ O ₁₂ ) * 4H ₂ O,

Ca ₃ (PO ₃ ) ₆ ^* 10H ₂ O, Ca ₄ P ₈ O ₂₄ ^* 16H ₂ O, Ca ₂ P ₂ O ₇ ^* 2H ₂ O, Ca ₂ (P ₄ O ₁₂ ) ^* 4H ₂ O,

Ca ₂ P ₂ O ₇ * 4H ₂ O, Ca ₃ (PO ₄₎ ₂ ^* xH ₂ 0, CaAIH (PO ₄₎ ₂ ^* 6H ₂ 0, Ca ₈ H ₂ (PO ₄₎ ₆₎ ^* 5H ₂ O, Ca ₄ H (PO ₄ ) ₃ ^* 5H ₂ O, Ca ₃ H ₂ (P ₂ O ₇ ) ₂ ^* 4H ₂ O, Ca ₁ , ₅ HP ₂ O ₇ ^* 2H ₂ O _l Ca (H ₂ PO ₄ ) ₂ ^* H ₂ O, Ca ₃ H ₂ (P ₂ 0 ₇₎ ₂ ^* H ₂ O,

Cerium phosphate CePO ₄ , CeP ₂ O ₇ , Ca (PO ₃ ) ₄ , CaP ₅ O ₄ , CeP ₃ O ₉ , Ce ₄ (P ₂ O ₇ ) ₃ ,

Calcium phosphate alpha, beta, gamma Ca ₂ P ₂ O ₇ , CaP On, Ca ₂ P ₆ O ₇ , alpha CaP ₄ On, Ca ₃ (P ₅ O ₄ ) ₂ , beta, delta, gamma Ca (PO ₃ ) ₂ , alpha, beta-Ca-P ₂ O ₆ , Ca ₄ P ₆ O ₁₉ , alpha-, beta-, gamma-Ca ₃ (PO ₄ ) ₂ , Ca _{x + 2} P _2x O ₆ x _{+ 2} ,

Cerium phosphate CePO ₄ , CeP ₂ 0 ₇ , Ca (PO ₃ ) ₄ , CeP ₅ 0 ₁₄ , CeP ₃ O ₉ , Ce ₄ (P ₂ 0 ₇ ) ₃ , CeP ₅ O ₁₄ , ceric hydrogen phosphate CeH ₂ P ₂ 0 ₈ ,

Lithium phosphate hydrate LiPO ₁₂ * 4H ₂ O, Li ₈ P ₈ O ₂₄ ^* 10H ₂ O, Li ₆ P ₆ O ₈ ^* 6H ₂ O,

Li ₆ P ₈ 0 ₂₄ ^* 6H ₂ 0, Li ₄ P ₄ 0 ₂ * nH ₂ 0, Li ₆ P ₆ Oi ₈ * nH ₂ 0, Li ₃ P ₃ O ₉ * 3H ₂ 0,

Lithium hydrogen phosphate Li ₃ HP ₂ 0 ₇ ^* H ₂ O,

Magnesium phosphate hydrate Mg P ₈ O ₂₄ * 19H ₂ O, Mg ₂ P ₄ O ₂ * 8H ₂ O, Mg ₃ (PO ₄ ) ₂ ^* nH ₂ O, Mg ₂ P ₂ O ₇ ^* 2H ₂ O,

Magnesium hydrogen phosphate hydrate MgHPO ₄ * nH ₂ O, Mg (H ₂ PO ₄ ) ₂ ^* nH ₂ O, Potassium phosphate hydrate K ₈ P ₈ O ₂₄ ^* 6H ₂ O, (KPO ₃ ) ₄ ^* 2H ₂ O, K ₆ P ₆ O ₁₈ ^* 3H ₂ O, alpha-, beta-K ₅ P ₃ O ₁₀ * nH ₂ O, K ₁₀ Pio0 ₃ 0 * 4H ₂ 0, K ₄ P ₂ O ₇ ^* nH ₂ 0, K ₅ P ₃ O ₁₀ ^* nH ₂ O,

K ₃ P0 ₄ * nH ₂ O, K ₁₀ P ₆ O ₂₀ ^* H ₂ O,

Potassium aluminum phosphate hydrate K ₆ Al ₂ P ₆ O ₂ i ^* 12H ₂ O,

Potassium hydrogenphosphate hydrate K ₂ H ₂ P ₂ O ₇ * nH ₂ O, K ₃ H ₂ P ₂ O ₇ ^* 0.5H ₂ O,

KH ₃ P ₂ O ₇ ^* H ₂ O, K ₃ H ₂ P ₃ O ₁ O * H ₂ O, ^ HPsO ^ x HsO, KH ₃ (PO ₄ ) ₂ ^* ₂ H ₂ O,

K ₂ H ₃ P ₃ O ₁₀ * 2H ₂ O, K ₃ HP ₂ O ₇ * 3H ₂ O, K ₂ HPO ₄ * 3H ₂ O, K ₃ HP ₂ O ₇ ^* 3H ₂ O,

Sodium hydrogenphosphate hydrate Na ₃ HP ₂ O ₆ ^* 9H ₂ O, Na ₃ HP ₂ O ₇ ^* H ₂ O,

Nä ₂ H ₂ P ₂ O ₇ .6H ₂ 0, Na ₂ H ₂ P ₂ 0 ₆ ^* 6H ₂ O, NaH ₂ PO ₄ ^* 12H ₂ 0, NaH ₂ PO ₄ ^* H ₂ O,

NaH ₃ P ₂ O ₆ * xH ₂ O, beta-Na ₂ HPO ₄ ^* 12H ₂ O, Na ₃ H ₂ P ₃ O ₁₀ ^* 1, 4H ₂ O,

2NaH ₂ PO ₄ * Na ₂ HPO ₄ * 2H ₂ O, NaH ₂ PO ₄ * 2H ₂ O, NaH ₂ PO ₂ ^* H ₂ O, Na ₂ HPO ₄ ^* nH ₂ O, Na ₄ HP ₃ O ₁₀ * H ₂ O, Na ₂ HPO ₃ * 5H ₂ O, Na ₃ HP ₂ 0 ₇ * nH ₂ O, Na ₃ H ₂ P ₃ O ₁₀ ^* 1, 5H ₂ O, sodium hydrate phosphate Na ₃ P ₃ O ₉ * nH ₂ 0, Na ₅ P ₃ O ₀ ^* 6H ₂ O, (NaPO ₃₎ ₃ ^* nH ₂ O, Na ₆ P ₆ 0 ₁₈ * 6H ₂ 0, Na ₅ (P ₅ 0 ₁₅₎ * 4H ₂ O, Na ₄ P ₂ O ₆ ^* nH ₂ O, Na ₄ P ₂ O ₇ * 10H ₂ O,

Na ₄ P ₄ Oi ₂ ^* 4H ₂ 0, (NaPO ₂₎ ₆ ^* nH ₂ O,

Sodium aluminum phosphate hydrate Na ₂ AIP ₃ Oi ₀ ^* 4H ₂ O, Na ₂ AIP ₂ O ₀ ^* 2H ₂ O,

Na ₂ AIP ₃ Oi ₀ , Na ₂ (AIP ₃ Oi ₀ ) ^* 2H ₂ O, Na ₃ Al (PO ₄ ) ₂ ^* 1, 5H ₂ O, Na ₂ Al 6P ₂ O ₁₅ ^* 10H ₂ O.

Preferred halogen-free flame retardant mixtures according to the invention which contain phosphate as non-combustible additive:

Component A 95 to 99.995 wt .-% Diethylphosphinsäuresalz and 0.005 to 5 wt .-% phosphate.

II) Halogen-free flame retardant mixture containing 10 to 90 wt .-% of a component A and 10 to 90 wt .-% aluminum phosphite, wherein

III) Halogen-free flame retardant mixture containing 20 to 80 wt .-% of a component A and 20 to 80 wt .-% aluminum phosphite, wherein Component A 95 to 99.995 wt .-% Diethylphosphinsäuresalz and 0.005 to 5 wt .-% phosphate.

Component A 99.3 to 99.95 wt .-% Diethylphosphinsäuresalz and 0.05 to 0.7 wt .-% phosphate.

The non-combustible additives may preferably also be

Organophosphonates act.

Preferred organophosphonates are those with cations of the alkali metals and with cations of protonated nitrogen bases z. B. of ammonia, primary, secondary, tertiary and quaternary amines and with cations of

Preferred organophosphonates are those with cations of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base.

Preferred organophosphonates are, for example, monoorganylphosphonates, such as

Mono- (Ci- ₈ alkyl) phosphonates, mono (C ₆ -C ₀ aryl) phosphonates, mono (C ₇ --i ₈ - aralkyl) phosphonates, particularly Monomethylphosphonate thereof,

Monoethyl phosphonates, monobutyl phosphonates, monohexyl phosphonates, monophenyl phosphonates, monobenzyl phosphonates, etc.

Preferred halogen-free flame retardant mixtures according to the invention which contain organophosphonate as non-combustible additive:

I) Halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% aluminum phosphite, wherein component A 95 to 99.995 wt .-% Diethylphosphinsäuresalz and 0.005 to 5 wt .-% Organophosphonat contains.

II) Halogen-free flame retardant mixture containing 0 to 90 wt .-% of a component A and 10 to 90 wt .-% aluminum phosphite, wherein

Component A contains from 95 to 99.995% by weight of diethylphosphinic acid salt and from 0.005 to 5% by weight of organophosphonate.

Component A contains 98 to 99.95% by weight of diethylphosphinic acid salt and 0.05 to 2% by weight of organophosphonate.

The non-combustible additives may preferably also be nitrates.

Preferably, the nitrates are those with cations of

Alkali metals and with cations of protonated nitrogen bases z. B. of ammonia, primary, secondary, tertiary and quaternary amines and with cations of alkaline earth metals; with cations of the elements of the third main group and with cations of the subgroup elements. Especially preferred

Subgroup elements are titanium, iron, zinc and mixtures thereof.

Preferred nitrates are those with cations of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base.

Preferred nitrates are aluminum nitrate (Al (NO ₃ ) 3), calcium nitrate (Ca (NO ₃ ) ₂ ), cerium (II) nitrate (Ce (NO ₃ ) ₂ ), cerium (III) nitrate (Ce (NO ₃ ) ₃ ) , Cerium (IV) nitrate (Ce (NO ₃ ) ₄ ), Cerium nitrate (Ce (N0 ₃₎ _x), iron nitrate (Fe (NO ₃₎ _x), iron (II) nitrate (Fe (NO ₃₎ _2),

Iron (III) nitrate (Fe (NO ₃ ) ₃ ), potassium nitrate (KNO ₃ ), lithium nitrate (LiNO ₃ ),

Magnesium nitrate (Mg _{/ 2} NO ₃ ), manganese (II) nitrate (Mni _{/ 2} NO ₃ ), manganese (III) nitrate (Mn- | _{/ 3} N0 ₃ ), manganese (IV) nitrate (Mni ₄ N0 ₃ ), sodium nitrate (NaNO ₃ ), titanium nitrate (Ti (NO ₃ ) _x ), titanium (II) nitrate (Tii _{/ 2} NO ₃ ), titanium (III) nitrate (Tii _{/ 3} NO ₃ ), titanium (IV) nitrate (Ti _{1 4} NO ₃ ), zinc nitrate (Zni ₂ NO ₃ ), tin nitrate (Sn (NO ₃ ) _x ), tin (II) nitrate (Sni _{/ 2} NO ₃ ), tin (IV) nitrate (Sni _{/ 4} NO ₃ ), zirconium nitrate ( Zr (NO ₃ ) x), zirconium (II) nitrate

(Zr _1/2 N0 ₃ ) and / or zirconium (IV) nitrate (Zr _1/4 NO ₃ ). Preferred halogen-free flame retardant mixtures according to the invention which contain nitrate as non-combustible additive:

Component A 95 to 99.995 wt .-% Diethylphosphinsäuresalz and 0.005 to 5 wt .-% nitrate.

Component A 99.79 to 99.99 wt .-% Diethylphosphinsäuresalz and 0.01 to 0.21 wt .-% nitrate. The non-combustible additives may preferably also be chlorides.

Preferred chlorides are those with cations of the alkali metals and with cations of protonated nitrogen bases z. B. of ammonia, primary, secondary, tertiary and quaternary amines and with cations of alkaline earth metals; with cations of the elements of the third main group; with cations of

Subgroup elements. Particularly preferred subgroup elements are titanium, iron, zinc and mixtures thereof.

Preferred chlorides are those with cations of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base

Preferred chlorides include:

Aluminum chloride acetate (C ₄ H ₆ AICIO), aluminum hydrogenchloride acetate,

Aluminum chloride AICI ₃ , aluminum chloride hydrate AICI ₃ ^* nH ₂ O,

Calcium acetate chloride hydrate C ₂ H ₃ CaCIO ₂ * nH ₂ O,

Calcium chloride CaCl ₂ , calcium chloride hydrate CaCl ₂ ^* nH ₂ O,

Hydrated iron chloride 2FeCI ₂ * nH ₂ 0, FeCl ₃ ^* nH ₂ O,

Iron magnesium chloride hydrate FeMgCl ₄ ^* nH ₂ O,

Iron _{manganese chloride} hydrate Mn _0i 5Feo, 5Cl ₂ * nH ₂ O,

Iron chloride hydrate FeZnCl ₄ * nH ₂ O, lithium chloride LiCl ^* nH ₂ O,

Magnesium chloride hydrate MgCl ₂ * nH ₂ O, titanium chloride hydrate TiCl ₃ * nH ₂ O,

Titanoxidchloridhydrat Ti ₂ 9O CI ₄₂ ₃₂ * ₀ H ₂ O, Ti ₂ O ₂ CI ₄ ^* 2H ₂ O,

Zinc chloride ZnCl ₂ ^* nH ₂ O,

Zinc aluminum chloride hydrate Zn ₂ Al (OH) ₆ Cl ^* 1, 8H ₂ O,

Zinc oxide chloride hydrate Zn ₂ OCI ₂ * 2H ₂ O, tin chloride hydrate SnCl ₄ * nH ₂ O, SnCl ₂ ^* nH ₂ O, zirconyl chloride hydrate ZrOCl ₂ ^* nH ₂ O,

Aluminum chloride hydroxide AI ₂ 9 (OH) ₇₈ Cl9, Aln (OH) ₃₀ Cl ₃ ,

Aluminum chloride hydroxide hydrate Ali ₃ CI ₁₅ (OH) ₂₄ ^* 37.5H ₂ O

Calcium hydroxide chloride, iron hydroxide chloride Fe ₆ Cl _2- x (OH) i _{2 + x} ,

Lithium hydroxide chloride Li ₂ Cl (OH), magnesium sulfate hydrochloride MgClOH,

Magnesium chloride hydroxide hydrate Mg ₂ (OH) ₃ Cl ^* 4H ₂ O, Zinc chloride hydroxide hydrate, tin hydroxide chloride Sn ₄ (OH) ₆ Cl 2,

Ferric chloride FeCl ₂ , FeCl ₃ , lithium chloride, magnesium chloride, manganese chloride

MnCl ₂ ,

Potassium chloride and potassium aluminum chloride.

Preferred halogen-free flame retardant mixtures according to the invention which contain chloride as non-combustible additive:

Component A 95 to 99.995 wt .-% Diethylphosphinsäuresalz and 0.005 to 5 wt .-% chloride.

Component A 99.5 to 99.99 wt .-% Diethylphosphinsäuresalz and 0.01 to 0.5 wt .-% chloride.

The non-combustible additives may preferably also be acetates.

Preferred acetates are those with cations of the alkali metals and with cations of protonated nitrogen bases z. B. of ammonia, primary, secondary, tertiary and quaternary amines and with cations of alkaline earth metals; with cations of the elements of the third main group; with cations of

Preferred acetates are those with cations of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base

According to the invention suitable acetates are about:

Aluminum acetate (Ali / 3 (C ₂ H ₄ O 2)), calcium acetate (Cai / ₂ (C ₂ H ₄ O 2)), cerium (II) acetate, cerium (III) acetate (Ce _{/ 3} (C ₂ H ₄ O ₂ )), Cerium (IV) acetate (Ce _{1 4} (C ₂ H ₄ O ₂ )), iron acetate

(Fe _x (C ₂ H 40 ₂ )), iron (II) acetate) (Fe _1/2 (C ₂ H ₄ O ₂ )), iron (III) acetate (Fei / ₃ (C ₂ H ₄ O ₂ )), potassium acetate ( K (C ₂ H ₄ O ₂ )), lithium acetate (Li (C ₂ H ₄ O ₂ )), magnesium acetate

(Mg ^^ F ^)), manganese acetate (Mn _x (C2H ₄ O ₂ )), manganese (II) acetate

(Mni / ₂ (C ₂ H ₄ O ₂ )), manganese (III) acetate (Mn _{/ 3} (C ₂ H 0 ₂ )), manganese (IV) acetate

(Mn _1/4 (C ₂ H ₄ O ₂ )), sodium acetate (Na (C ₂ H ₄ O ₂ )), titanium acetate, titanium (II) acetate,

Titanium (III) acetate, titanium (IV) acetate (Ti _{1 4} (C ₂ H ₄ O ₂ )), zinc acetate (Zn _{/ 2} (C ₂ H O ₂ )), tin (II) acetate (Sn _1/2 (C ₂ H ₂ O) _2)), tin (IV) acetate (Sn _1/4 (C ₂ H ₄ O _2)), tin acetate (Sn _x (C ₂ H ₄ O 2)), zirconium acetate (Zr _x (C2H ₄ O _2)), zirconium (II) acetate

(Zri / 2 (C2H ₄ O 2)), zirconium (III) acetate and / or zirconium (IV) acetate (Zri / ₄ (C ₂ H ₄ O ₂ )).

Preferred halogen-free flame retardant mixtures according to the invention which contain acetate as non-combustible additive: I) Halogen-free flame retardant mixture containing 1 to 99% by weight of a component A and 1 to 99% by weight of aluminum phosphite, where

Component A 95 to 99.995 wt .-% Diethylphosphinsäuresalz and 0.005 to 5 wt .-% acetate. II) Halogen-free flame retardant mixture containing 0 to 90 wt .-% of a component A and 10 to 90 wt .-% aluminum phosphite, wherein

Component A 95 to 99.995 wt .-% Diethylphosphinsäuresalz and 0.005 to 5 wt .-% acetate. III) Halogen-free flame retardant mixture containing 20 to 80 wt .-% of a component A and 20 to 80 wt .-% aluminum phosphite, wherein

Component A 95 to 99.995 wt .-% Diethylphosphinsäuresalz and 0.005 to 5 wt .-% acetate.

Component A 99.25 to 99.99 wt .-% Diethylphosphinsäuresalz and 0.01 to 0.75 wt .-% acetate.

The non-combustible additives may preferably also be sulfites. Preferred sulfites are those with cations of the alkali metals and with cations of protonated nitrogen bases z. B. of ammonia, primary, secondary, tertiary and quaternary amines and with cations of alkaline earth metals; with cations of the elements of the third main group; with cations of

Preferred sulfites are those with cations of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base Sodium metabisulfite, sodium sulfite, sodium bisulfite, potassium metabisulfite, potassium sulfite, potassium bisulfite and potassium hydrogen sulfate.

Preferred halogen-free flame retardant mixtures according to the invention, which contain sulfite as non-combustible additive:

I) Halogen-free flame retardant mixture containing 1 to 99 wt .-% of a component A and 1 to 99 wt .-% aluminum phosphite, wherein Component A 95 to 99.995 wt .-% Diethylphosphinsäuresalz and 0.005 to 5 wt .-% sulfite.

Component A 95 to 99.995 wt .-% Diethylphosphinsäuresalz and 0.005 to 5 wt .-% sulfite.

Component A 99.18 to 99.99 wt .-% Diethylphosphinsäuresalz and 0.01 to 0.82 wt .-% sulfite.

Overall, therefore, halogen-free flame retardant mixtures are preferred which contain 1 to 99 wt .-% of a component A and 1 to 99 wt .-% of a component B, wherein component A 95 to 99.995 wt .-% of a

Diethylphosphinsäuresalzes and 0.005 to 5 wt .-% of sulfates, phosphates, phosphonates, nitrates, chlorides, sulfites and / or acetates and it contains the component B is aluminum phosphite.

The term aluminum phosphite according to the invention covers a number of compounds, as defined below.

The aluminum phosphites according to the invention include an alkali-aluminum mixed phosphite of the formula

Al _2, ooM _z (HPO ₃ ) _y (OH) _v ^* (H ₂ O) _w (II) in the

M alkali metal ions,

z from 0.01 to 1, 5,

y 2.63 to 3.5,

v 0 to 2 and w 0 to 4,

means

Such an aluminum phosphite according to the invention is, inter alia, a mixture of Al ₂ (HPO ₃ ) ₃ * nH ₂ O (with n = 0-4) and sodium aluminum phosphite. The

Sodium aluminum phosphite corresponds to the formula (II), such. B. the

Molar formula AI _2, oNao, 6 (HPO ₃ ) 2.89 * 0.28H ₂ O.

The X-ray powder data of sodium aluminum phosphite are given in Example 78 and the X-ray powder data of Al ₂ (HPO 3) 3 ^* 4H ₂ O for comparison in Example 82.

Aluminum phosphite according to the invention is also a mixture of

0 - 99.9% by weight Al ₂ (HPO ₃ ) 3 ^* nH ₂ 0 and 0.1 - 100% by weight

Natriumaluminiumphosphit.

A preferred aluminum phosphite according to the invention is a mixture of

1-50% by weight of Al ₂ (HPO ₃ ) 3 * nH ₂ O and 1-50% by weight of sodium aluminum phosphite.

Most particularly preferred is an inventive aluminum phosphite of a mixture of 5-75 wt .-% Al ₂ (HPO ₃₎ ₃ ^* nH ₂ 0 and 5-25 wt .-%

Natriumaluminiumphosphit.

An aluminum phosphite which can be used according to the invention is also an alkali-aluminum mixed phosphite according to the formula

Al _x M _z (HPO ₃ ) _y (OH) _v * (H ₂ O) _W (II) in the x 1, 00 to 2.0,

M alkali metal ions,

z 0.01 to 2.7,

y 2.63 to 3.5,

v is 0 to 2 and w is 0 to 6,

However, a usable aluminum phosphite according to the invention is also a mixture of the following composition:

80-99.9% by weight of Al ₂ (HPO ₃ ) ₃

0.1-25% by weight of water

0-10% by weight of sulphate

0-15% by weight of sodium

0-10% by weight of phosphate Also usable according to the invention is an aluminum phosphite which is of the following composition:

80-99.9% by weight of Al ₂ (HPO ₃ ) ₃

0, 1 - 25 wt .-% water

0 - 14.8 wt .-% sodium sulfate

0 - 7.4 wt .-% sodium phosphate

The usable aluminum phosphites according to the invention also include the aluminum hydrogen phosphite of the formula (III)

Al ₂ , oo (HPO ₃ ) _u (H ₂ PO ₃ ), ^* (H ₂ O) _s (III) in the

u 2 to 2.99,

2 to 0.01 and

s 0 to 4 means. Aluminum phosphite which can be used according to the invention is also a mixture of aluminum phosphite with sparingly soluble aluminum salts and nitrogen-free foreign ions containing 80 to 99.898% by weight of aluminum phosphite of the formula (I)

Al ₂ (HPO ₃ ) ₃ ^* H ₂ O (I) wherein

x 0 to 4 means

0.1 to 10 wt .-% sparingly soluble aluminum salts and

0.002 to 10 wt .-% of nitrogen-free foreign ions.

Preferably, the sparingly soluble aluminum salts are

Aluminum hydroxide, aluminum hydroxychloride,

Polyaluminum hydroxy compounds, aluminum carbonates, hydrotalcites

(Mg ₆ Al ₂ (OH) ₁₆ CO ₃ ^* nH ₂ O), dihydroxyaluminum sodium carbonate (NaAl (OH) ₂ CO ₃ ), aluminas, alumina hydrate, mixed alumina hydroxides, basic aluminum sulfate and / or alunite.

Preferably, the nitrogen-free foreign ions are chlorides, complex chlorides, bromides; hydroxides, peroxides, peroxide hydrate, sulphites, sulphates, sulphate hydrates, acid sulphates, hydrogen sulphates, peroxosulphates,

Peroxodisulfate; to nitrates; carbonates, percarbonates, stannates; Borates, perborates, perborate hydrates; formates, acetates, propionates, lactates and / or ascorbates and / or cations of the elements Li, Na, K, Mg, Ca, Ba, Pb, Sn, Cu, Zn, La, Ce, Ti, Zr, V, Cr , Mn, Fe, Co and / or Ni.

Furthermore, aluminum phosphite which can be used according to the invention is also a

Mixture of aluminum hydrogen phosphites of the formula (III)

Al ₂ , oo (HPO ₃ ) _u (H ₂ PO ₃ ) t ^* (H ₂ O) _s (III) with aluminum salts, containing

91 to 99.9% of aluminum hydrogen phosphites of the formula (III) 0.1 to 9% aluminum salts and

0 to 50% (crystal) water

in formula (III)

u 2 to 2.99,

t 2 to 0.01 and

s 0 to 4 means.

The aluminum phosphites which can be used according to the invention include, inter alia, aluminum phosphite (Al (H ₂ PO ₃ ) 3), secondary aluminum phosphite, basic aluminum phosphite (Al (OH) (H ₂ PO ₃ ) ₂ ^* 2aq),

Aluminum phosphite tetrahydrate (Al ₂ (HPO ₃ ) ₃ ^* 4aq), Al ₇ (HPO ₃ ) ₉ (OH) 6 (1,6-hexanediamine) _1i5 * 12H ₂ 0, Al ₂ (HPO ₃ ) ₃ * xAl ₂ O ₃ * nH ₂ O with x = 2.27-1 and / or Al ₄ H ₆ P ₁₆ O ₁₈ . The residual moisture of the halogen-free invention is preferably

Flame retardant mixture 0.01 to 10 wt .-%, in particular 0.1 to 2 wt .-%.

The average particle size d _{50 of} the halogen-free flame retardant mixture according to the invention is preferably from 0.1 to 1000 μm, in particular from 10 to 100 μm.

The bulk density of the halogen-free invention is preferably

Flame retardant mixture 80 to 800 g / l, in particular 200 to 700 g / l. The flowability of the halogen-free invention

Flame retardant mixture is determined according to Pfrengle (DIN ISO 4324 surfactants, powders and granules, determination of Schüttwinkels, Dec. 1983, Beuth Verlag Berlin). Thereafter, the aforementioned flowability is determined by determining the height of the cone of a powder or granules or the ratio of bevel radius to cone height. The cone is generated by passing a special amount of the substance to be examined in a defined apparatus a special funnel is poured out. The defined bevel radius is created by pouring the cone until the product overflows over a circular plate raised from the ground. The radius of the plate is fixed. The funnel has an inside diameter of 10 mm. The plate has a radius of 50 mm. 5 determinations are carried out and averaged. The height is measured in millimeters with a measuring strip from the plate, measured to the apex of the cone. The ratio of bevel radius (50 mm) to cone height is calculated from the mean value. On a halogen-free flame retardant mixture according to the prior art, bulk cone heights of 29.9 to 49.9 mm corresponding to a span of 20 mm were determined and ratios of radius to height (= cot alpha) of 1.67 to 1.00 corresponding to a span of 0.67. The halogen-free flame retardant mixtures according to the invention can be prepared by various methods.

Preferably, aluminum diethylphosphinate is mixed directly with the non-combustible additive and aluminum phosphite.

Also preferably, aluminum diethylphosphinate containing the non-combustible additive is mixed with aluminum phosphite.

In the present invention, the aluminum diethylphosphinate containing the non-combustible additive is prepared by reacting diethylphosphinic acid with elemental metal or a metal salt at 0 to 300 ° C for 0.01 to 1 hours.

Preferred metal salts are metal oxides, mixed metal oxide hydroxides, hydroxides, etc.

In another embodiment of the invention, the non-combustible additive-containing aluminum diethylphosphinate is prepared by reacting a Diethylphosphinsäure with a free base for 0.01 to 1 hours at 0 to 300 ° C.

In another embodiment, the non-combustible additive-containing Aluminiumdiethylphosphinat is prepared by a

Diethylphosphinsäure in the form of an alkali metal salt with a salt of the desired cation for 0.01 to 1 hours at 0 to 300 ° C.

Preferred alkali metal salts are sodium and potassium salts.

Preferred salts which provide the desired cations are acetates, hydroxoacetates, chlorides, hydroxochlorides, nitrates, sulfates, hydroxosulfates, phosphonates and phosphites. Their concentration in aqueous solution is preferably from 5 to 95% (anhydrous solid), more preferably from 20 to

50% by weight.

Diethylphosphinsäure in the form of a reactive derivative with a derivative of the desired cation for 0.01 to 1 hours at 0 to 300 ° C. Preferred diethylphosphinic acid derivatives are diethylphosphinic esters, pyroesters, chlorides, phosphates, acetates, phenolates, etc.

In the embodiment in which the aluminum diethylphosphinate

Contains dialkylphosphinic telomers as a non-combustible additive, the dialkylphosphinic telomer content is 50 ppm to 15 wt .-%, more preferably 1000 ppm to 8 wt .-%.

In the embodiment in which the aluminum diethylphosphinate contains sulfate as a noncombustible additive, the sulphate content is from 50 ppm to 5% by weight, more preferably from 100 ppm to 9000 ppm. In the embodiment in which the aluminum diethylphosphinate contains phosphate as a non-combustible additive, the phosphate content is 50 ppm to

5 wt .-%, more preferably 500 ppm to 7000 ppm. In the embodiment in which the aluminum diethylphosphinate

Organylphosphonat contains as a non-combustible additive is the

Organylphosphonate content 50 ppm to 5 wt .-%, particularly preferably 500 ppm to 2 wt .-%. In the embodiment in which the aluminum diethylphosphinate contains nitrate as a nonflammable additive, the nitrate content is 50 ppm to 5 wt%, more preferably 100 ppm to 2100 ppm.

In the embodiment in which the aluminum diethylphosphinate contains chloride as the non-combustible additive, the chloride content is 50 ppm to 5 wt%, more preferably 100 ppm to 5000 ppm.

In the embodiment in which the aluminum diethylphosphinate contains acetate as the non-combustible additive, the acetate content is 50 ppm to 5 wt%, more preferably 100 ppm to 7500 ppm.

In the embodiment in which the aluminum diethylphosphinate contains sulfite as the non-combustible additive, the acetate content is 50 ppm to 5 wt%, more preferably 100 ppm to 8200 ppm.

The invention also encompasses flame-retardant polymer molding compositions containing 1 to 50% by weight of the halogen-free compounds according to the invention

Flame retardant mixture

1 to 99% by weight of polymer or mixtures thereof,

0 to 60 wt .-% additives and

0 to 60 wt .-% filler. The invention preferably comprises flameproofed polymer molding compositions containing

5 to 30 wt .-% of the halogen-free invention

Flame retardant mixture,

15 to 85% by weight of polymer or mixtures thereof,

From 5 to 40% by weight of additives and

5 to 40 wt .-% filler.

The polymers preferably originate from the group of thermoplastic polymers such as polyester, polystyrene or polyamide and / or the thermosetting polymers.

The polymers are preferably polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene, and also polymers of

Cycloolefins such. From cyclopentene or norbornene; also polyethylene (which may be optionally crosslinked), e.g. High density polyethylene (HDPE), high density polyethylene (HDPE-HMW), high density polyethylene and ultrahigh molecular weight (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene Density (LLDPE), branched low density polyethylene (VLDPE), as well as mixtures thereof.

Preferably, the polymers are copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as. B. ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and

Blends thereof with low density polyethylene (LDPE), propylene-butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers, ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, Ethylene-octene copolymers, propylene-butadiene copolymers,

Isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and their

Copolymers with carbon monoxide, or ethylene-acrylic acid copolymers and their salts (ionomers), as well as terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidenenorbornene; further

Mixtures of such copolymers with one another, for. 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 random construction

Polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers such. B. polyamides. The polymers are preferably hydrocarbon resins (eg C5-C9) including hydrogenated modifications thereof (eg tackifier resins) and mixtures of polyalkylenes and starch.

The polymers are preferably polystyrene (polystyrene 143E (BASF), poly (p-methylstyrene), poly (alpha-methylstyrene).

Preferably, the polymers are copolymers of styrene or alpha-methylstyrene with dienes or acrylic derivatives, such as. Styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate

and methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; Blends of high impact strength of styrene copolymers and another polymer, such as. A polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; and block copolymers of styrene, such as. Styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.

Preferably, the polymers are graft copolymers of styrene or alpha-methylstyrene, such as. Styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (resp.

Methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and methyl methacrylate

polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; Styrene and maleimide on polybutadiene, styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate-butadiene copolymers, and mixtures thereof, as described, for. B. known as so-called ABS, MBS, ASA or AES polymers.

The polymers are preferably halogen-containing polymers, such as. As polychloroprene, chlorinated rubber, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or chlorosulfonated

Polyethylene, copolymers of ethylene and chlorinated ethylene,

Epichlorohydrin homopolymers and copolymers, in particular polymers

halogen-containing vinyl compounds, such as. B. polyvinyl chloride,

Polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; As well as their

Copolymers, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.

The polymers are preferably polymers which are derived from alpha, beta-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, polymethyl methacrylates which have been modified with butyl acrylate, polyacrylamides and polyacrylonitriles and copolymers of said monomers with one another or with other unsaturated monomers , such as Acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers. The polymers are preferably polymers which are derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate,

Polyvinyl butyral, polyallyl phthalate, polyallylmelamine; and their copolymers with olefins.

The polymers are preferably homo- and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers. The polymers are preferably polyacetals, such as

Polyoxymethylene, as well as those polyoxymethylenes, the comonomers, such as. For example, ethylene oxide; Polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

The polymers are preferably polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides. The polymers are preferably polyurethanes derived from polyethers, polyesters and polybutadienes having terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other hand, and precursors thereof. The polymers are preferably 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, ^Nylon® 4, Fa. DuPont), polyamide 4/6

(Poly (tetramethylene adipamide), poly (tetramethylene-adipamide), Nylon ^® 4/6, Fa. DuPont), polyamide 6 (polycaprolactam, poly-6-aminohexanoic acid, Nylon ^® 6, Fa. DuPont, Akulon ^® K122, from DSM;. Zytel ^® 7301, from DuPont;... Durethan ^® B 29, from Bayer), polyamide 6/6 ((poly (N, N'-hexamethyleneadipinediamid), nylon ^® 6/6, DuPont, Zytel ^® . 101, DuPont;. Durethan ^® A30, Durethan ^® AKV, Durethan ^® AM, from Bayer; Ultramid ^® A3, BASF), polyamide 6/9 (poly (hexamethylene nonanediamid), nylon 6/9 ^®, DuPont. ), Polyamide 6/10 (poly (hexamethylene sebacamide), nylon ^® 6/10, from DuPont), polyamide 6/12 (poly (hexamethylene dodecanediamide), nylon ^® 6/12, from DuPont), polyamide 6/66 (Poly (hexamethylene adipamide-co-caprolactam), nylon ^® 6/66, from DuPont), polyamide 7 (poly-7-aminoheptanoic acid, nylon ^® 7, from DuPont), polyamide 7/7

(Polyheptamethylenpimelamid, Nylon ^® 7/7, Fa. DuPont), polyamide (poly aminooctanoic acid-8, nylon ^® 8, Fa. DuPont) 8, polyamide 8/8

(Polyoctamethylensuberamid, Nylon ^® 8/8, Fa. DuPont), polyamide (poly-9- aminononanoic acid, Nylon ^® 9, Fa. DuPont) 9, polyamide 9/9 7

(Polynonamethylenazelamid, Nylon ^® 9/9, Fa. DuPont), polyamide 10 (poly-10-amino-decanoic acid, Nylon ^® 10, Fa. DuPont), polyamide 10/9

(Poly (decamethylene azelamide), nylon 10/9 ^®, Fa. DuPont), polyamide 10/10

(Polydecamethylensebacamid, Nylon ^® 10/10 Fa. DuPont), polyamide (aminoundecanoic acid, poly-11, Nylon ^® 1, Fa. DuPont) 11, polyamide 12 (polylauryllactam, Nylon ^® 12, Fa. DuPont, Grillamid ^® L20, Fa Ems Chemie), aromatic polyamides starting from m-xylene, diamine and adipic acid; Polyamides prepared from hexamethylenediamine and isophthalic and / or terephthalic acid

(Polyhexamethylenisophthalamid polyhexamethylene terephthalamide) and optionally an elastomer as a modifier, for. As 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, such as. With polyethylene glycol,

Polypropylene glycol or polytetramethylene glycol. Further modified with EPDM or ABS polyamides or copolyamides; and during processing condensed polyamides ("RIM polyamide systems").

It is also possible to use aromatic polyamides such as PA4T, PA6T,

PA9T, PA10T, PA11T and / or MXD6, amorphous polyamides such as 6I / X and TPE-A "rigid" and "soft".

The polymers are preferably also polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and

Polybenzimidazoles.

The polymers are preferably polyesters which differ from

Derive dicarboxylic acids and dialcohols and / or hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate,

Polybutylene terephthalate (Celanex ^® 2500, Celanex ^® 2002, from Celanese;. Ultradur ^®, BASF), poly-1, 4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates, and also block polyether esters derived from hydroxyl-terminated polyethers; also with polycarbonates or MBS modified polyester. The polymers are preferably polycarbonates and polyestercarbonates and also polysulfones, polyethersulfones and polyetherketones. The polymers are preferably crosslinked polymers which are derived from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins. Preferably, the polymers are drying and non-drying alkyd resins.

The polymers are preferably unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids

derived polyhydric alcohols, and vinyl compounds as crosslinking agents, as well as their halogen-containing, flame-retardant modifications.

Preferably, the polymers are crosslinkable acrylic resins derived from substituted acrylic acid esters, such as. B. of epoxy acrylates,

Urethane acrylates or polyester acrylates.

The polymers are preferably alkyd resins, polyester resins and acrylate resins which are blended with melamine resins, urea resins, isocyanates,

Isocyanurates, polyisocyanates or epoxy resins are crosslinked.

The polymers are preferably crosslinked epoxy resins which are derived from aliphatic, cycloaliphatic, heterocyclic or aromatic

Derive glycidyl compounds, for. B. products of bisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, by conventional hardeners such. As anhydrides or amines can be crosslinked with or without accelerators.

Preferably, the polymers are mixtures (polyblends) of the aforementioned polymers, such as. As PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT,

PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, P PO / PA 6.6 and copolymers,

PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

Preferred additives for the halogen-free invention

Flame retardant mixtures are z. B. synergists.

According to the invention, the synergists used are melamine phosphate, dimelamine phosphate, pentamelamine triphosphate, trimelamine diphosphate, tetrakis melamine triphosphate, hexakismelamine pentaphosphate, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphates, melampolyphosphates,

Melamine polyphosphates and / or melon polyphosphates are preferred. Furthermore, as synergists melamine condensation products such as melam, Meiern and / or melon are preferred.

According to the invention, further preferred synergists are oligomeric esters of tris (hydroxyethyl) isocyanurate with aromatic polycarboxylic acids,

Benzoguanamine, tris (hydroxyethyl) isocyanurate, allantoin, glycouril, melamine, melamine cyanurate, urea cyanurate, dicyandiamide and / or guanidine.

According to the invention, synergists are furthermore preferably nitrogen-containing

Phosphates of the formulas (NH ₄ ) _y H _3-y P0 ₄ or (NH ₄ PO ₃ ) ₂ , where y is 1 to 3 and z is 1 to 10,000

Preferred further additives in the flame retardant compositions of the invention are zinc compounds, e.g. Zinc oxide, zinc hydroxide,

Tin oxide hydrate, zinc carbonate, zinc stannate, zinc hydroxystannate, basic zinc silicate, zinc phosphate, zinc borate, zinc molybdate or zinc sulfides. Preferred further additives in the flame retardant compositions according to the invention are those from the group of carbodiimides and / or (poly) isocyanates. Preferred further additives are from the group of sterically hindered phenols (e.g., B. Hostanox OSP ^® 1), sterically hindered amines, and

Light stabilizers (z. B. Chimasorb ^® 944, Hostavin ^® types), phosphonites and antioxidants (eg. B. Sandostab ^® P-EPQ of Fa. Clariant) and release agent

(Licomont ^® grades from. Clariant).

Preferred further fillers in the flame retardant compositions according to the invention are oxygen compounds of silicon,

Magnesium compounds, e.g. B. metal carbonates of metals of the second

Main group of the Periodic Table, magnesium oxide, magnesium hydroxide, hydrotalcites, dihydrotalcite, magnesium carbonates or magnesium calcium carbonates, calcium compounds, eg. Calcium hydroxide, calcium oxide,

Hydrocalumite, aluminum compounds, eg. Example, alumina, aluminum hydroxide, boehmite, gibbsite or aluminum phosphate, red phosphorus, zinc or

Aluminum compounds; as well as glass fibers and glass balls.

Compounding units which can be used according to the invention

Multi-zone screw extruder with three-zone screws and / or

Short compression screws; also Ko-kneader z. B. Fa. Coperion Buss Compounding Systems, CH-Pratteln, z. B. MDK / E46-11 D and / or laboratory kneader (MDK 46 Buss, Switzerland with L = 11 D).

Compounding units which can be used according to the invention are also

Twin screw extruder, z. Coperion Werner & Pfleiderer GmbH & Co. KG, Stuttgart (ZSK 25, ZSK30, ZSK 40, ZSK 58, ZSK MEGAcompounder 40, 50, 58, 70, 92, 119, 177, 250, 320, 350, 380) and / or Berstorff GmbH, Hanover, Leistritz Extrusionstechnik GmbH, Nuremberg. Compounding units that can be used in accordance with the invention are ring extruders, eg. B. the Fa. 3 + extruder GmbH, running, with a ring of three to twelve small screws that rotate around a static core and / or

Planetary roller extruder, z. B. the Fa. Entex, Bochum and / or degassing extruder and / or cascade extruder and / or Maillefer-Peck.

Compounding units which can be used according to the invention are compounders with counter-rotating twin screw z. B. Compex 37- or -70 types of the company. Krauss -Maffei Berstorff.

Effective screw lengths according to the invention are 20 to 40D in single-screw extruders or single-screw extruders.

Effective screw lengths (L) according to the invention

Mehrzonenschneckenextudern are z. Eg 25D with feed zone (L = 10D),

Transition zone (L = 6D), discharge zone (L = 9D).

Screw lengths effective in accordance with the invention in twin-screw extruders are 8 to 48D.

Production, processing and testing of flame-retardant polymer molding compounds and plastic moldings.

The flame retardant components are mixed with the polymer granulate and any additives and via the side feeder of a twin-screw extruder (Leistritz ZSE 27 / 44D type) at temperatures of 230 to 260 ° C

(glass fiber reinforced PBT), 260 - 310 ° C in PA 6.6 or at 250 - 275 ° C in PA 6 incorporated. The glass fibers were over a second side feed

added. The homogenized polymer strand was stripped off, cooled in a water bath and then granulated.

After sufficient drying, the molding materials were on a

Injection molding machine (type Arburg 320 C Allrounder) at melt temperatures of 240 to 300 ° C to test specimens processed and based on the UL 94 test

(Underwriter Laboratories) tested for flame retardancy and classified.

Identification of telomeres and determination of their content:

The ³¹ P NMR spectra are measured with a Jeol JNM-ECS-400 instrument, a 400 MHz NMR instrument from JEOL (Germany) GmbH. A sample of

100 - 150 mg is dissolved in 2 ml of 10 wt .-% NaOD / D ₂ O by gently warming the sample to about 40 ° C. The measurement is performed in { ¹ H} decoupling mode with 2048 scans.

With reference to Table 9, the ³¹ P NMR signals of the telomers can be taken from a ³¹ P NMR spectrum. The ³ P NMR integration values give the percentage of ³ P nuclei relative to all ³¹ P nuclei in the sample. These values are multiplied for each substance by an individual factor (f = MW (telomer as Al salt) divided by 3 * AG (phosphorus) [MW: molecular weight, WG: atomic weight].) All such values plus the value for the diethylphosphinate salt The values for each isomer multiplied by 100 and divided by the subtotal gives the telomeric content in wt%.

The assignment of the chemical structures of the telomers to the ³¹ P NMR signals can be done by combining the ³¹ P NMRs and a) the intensities of the signals with LC / MS (combination of liquid chromatography and mass spectroscopy analysis), b) by targeted Synthesis of telomeres and backfilling of ³¹ P samples with reference materials thus obtained or c) by combination of ³¹ P NMR and ¹³ C NMR spectroscopy.

Diethyiphosphinate with molecular weight 122 g / mol is the most intense peak in LC-MS and also in ³¹ P-NMR. Molecular mass 122 admits only the structure diethyiphosphinate, the ³¹ P NMR chemical shift found is listed in Table 9.

n-butyl ethyl phosphinate and sec-butyl ethyl phosphinate have the LC-MS

Molecular weight 150 g / mol. This molecular weight leaves only the structure

"N-butyl ethyl phosphinate" and "sec-butyl ethyl phosphinate" to. n-butyl is in LC / MS and more intense in P-NMR than sec-butyl. Consequently, the more intense signal (to the right of diethyl) is the n-butyl ethyl phosphinate, the less intense signal (to the left of diethyl) the sec-butyl ethyl phosphinate. The signal layers found are listed in Table 9.

Aluminum tri (n-butylethylphosphinate) can be chemically prepared in several steps by butyl group addition to hypophosphorous acid, hereinafter

Ethylgruppenanlagerung, formation of Butylethylphosphinsäure-Na-salt with sodium hydroxide solution and reaction with Al-sulfate solution in H ₂ 0. The product can be used to identify n-butyl ethylphosphinate in unknown samples by replenishment. The identity of the alkyl groups is thus clearly dictated by the choice of raw materials. sec-Butylethylphosphinate can be identified by recording a ³ C-NMR and a DEPT-135 spectrum. "DEPT" stands for Distortionless Enhancement by Polarization Transfer and is a useful method to distinguish between CH, CH ₂ and CH ₃ groups.

The CH group characteristic of the sec-butyl group (-CH (-CH ₃ ) -CH ₂ -CH ₃ ) gives a signal at 33.7 ppm (with a Jpc coupling of 91 Hz) ¹ Jpc coupling defined as the coupling of the phosphorus core via a covalent bond to the next carbon nucleus.

Table 9: ³¹ P NMR chemical shift of telomeres

example 1

An aluminum diethylphosphinate containing telomeres as an additive is prepared by dissolving 2.2 kg (20.7 moles) of sodium hypophosphite 1-hydrate in 8 kg (7.62 liters) of acetic acid and precipitating out in a 16 liter jacketed pressure reactor Steel enamel submitted. After the reaction mixture had been heated to 85 ° C., ethylene was introduced into the reactor through a reducing valve set at 7 bar until saturation. The reaction was carried out with constant stirring by metering in a solution of 56 g

(1 mol%) of 2,2'-azobis (2-amidinopropane) dihydrochloride in 250 ml of water started and controlled by the radical initiator dosing speed so that the

Reaction temperature in the reactor at a jacket temperature of 80 ° C with constant supply of ethylene at an average pressure of about 7 bar did not rise above 95 ° C. The dosing time was a total of 3 hours. Then allowed to react for 3 h at 85 ° C. The reactor was relaxed and on

Room temperature cooled. The resulting solution was on the rotary evaporator largely from

Dissolved solvent acetic acid and then treated with 15.9 liters of water. Within three hours, 4333 g (6.9 mol Al) of an aqueous

Aluminum sulfate solution with 4.3 wt .-% AI content added. Subsequently, the solid obtained was filtered off, washed successively 2 times with 2 l of water and dried at 130 ° C in vacuo.

The product contains 15.9 wt .-% Aluminiumbutylethylphosphinat and 0.2 wt .-% residual moisture. Example 2

According to Example 1 is 3 bar ethylene pressure and 95.2 g

Sodium peroxodisulfate worked. The product contains 5.8% by weight of aluminum ethylphosphonate. Example 3

800 g of a solution obtained as in Example 1 is added after

Relax and cool down with 2500 ml of acetic acid and then add 42 g (0.54 mol) of aluminum hydroxide. It was then refluxed for about 4 hours, cooled and filtered off. The resulting solid was washed with 1 liter of glacial acetic acid and then dried at 130 ° C in vacuo. The product contains 5.8% by weight of aluminum acetate.

Example 4 (comparison)

Aluminum diethylphosphinate and aluminum phosphite (amounts in Table 1) are weighed into a polyethylene bottle so that about 1 kg

Flame retardant mixture results. In an overhead mixer, mix for about 2 hours until homogeneity is achieved.

Examples 5 to 13

Aluminiumdiethylphosphinat containing an additive of telomeres, with aluminum phosphite (amounts in Table 1) in a polyethylene bottle so

weighed in that each results in about 1 kg of flame retardant mixture and these mixed in an overhead mixer for about 2 hours until homogeneity is reached. Experiments show a more uniform flowability in the products of Examples 5 to 13 than in the product without additives from Comparative Example 4. Particularly good results show the combinations of aluminum butyl ethyl phosphinate and secondary aluminum phosphite (Example 6) or from aluminum butyl ethyl phosphinate and alkali aluminum -Mischphosphit

(Example 12).

Examples 14 and 5

Aluminiumdiethylphosphinat containing an addition of telomeres, with mixtures of Al2 (HPO ₃ ) 3 ^* 4H ₂ O and sodium aluminum phosphite from Example 80 or 81, which were previously dried at 220 ° C to 0.5 wt .-% residual moisture, weighed into a polyethylene bottle so that approx. 1 kg of flame retardant mixture is obtained and mixed in an overhead mixer for approx. 2 hours, until

Homogeneity is achieved.

Examples 16 to 24

Aluminiumdiethylphosphinat containing an additive of sulfate, is with

Weighed aluminum phosphite into a polyethylene bottle so that approx. 1 kg of flame retardant mixture is obtained and mixed in an overhead mixer for approx. 2 hours until homogeneity is achieved. Experiments show a more even flowability in the products of Examples 16 to 24 than in the product without additives from Comparative Example 4.

Examples 25 to 33

Aluminiumdiethylphosphinat containing an addition of phosphate is weighed with aluminum phosphite in a polyethylene bottle so that results in about 1 kg flame retardant mixture and mixed in an overhead mixer for about 2 hours until homogeneity is reached. Experiments show a more uniform flowability in the products of Examples 25 to 33 than in the product without additives from Comparative Example 4.

Examples 34 to 42 Aluminiumdiethylphosphinat containing an addition of phosphonate is weighed with aluminum phosphite in a polyethylene bottle so as to give about 1 kg flame retardant mixture. In an overhead mixer, mix is mixed for about 2 hours until homogeneity is achieved. The experiments show more uniform flowability than without additives in Comparative Example 4.

Examples 43 to 51

Aluminiumdiethylphosphinat containing an additive of nitrate, is with

Weighed aluminum phosphite into a polyethylene bottle so as to give about 1 kg of flame retardant mixture. In an overhead mixer, mix is mixed for about 2 hours until homogeneity is achieved. The experiments show more uniform flowability than without additives in Comparative Example 4.

Examples 52 to 60

Aluminiumdiethylphosphinat containing an addition of chloride, is with

Examples 61 to 69

Aluminiumdiethylphosphinat containing an additive of acetate, is with

Example 70

According to the general procedure is a mixture of 50 wt .-% polyamide 6.6, 20 wt .-% halogen-free flame retardant mixture from Example 12 and

30 wt .-% glass fibers processed into a flame-retardant polymer molding composition. After drying, the molding compositions on an injection molding machine to Processed polymer molding. A UL-94 classification of V-0 was determined.

Examples 71 to 77

According to Example 70, flame-retardant polymer molding compositions based on polyamide 6, polyamide 4.6 and polybutylene terephthalate are processed. After drying, the molding compositions on an injection molding machine to

Processed polymer molding. A UL-94 classification of V-0 was determined.

Table 1: Flame retardant mixtures of Diethylphosphinsäuresalz, telomeres and Aluminiumphosphlt

Example 4 Comparison 5 6 7 8 9 10 1 1 12 13 14 15

Diethylphosphinic acid 80 99 99 1 90 90 10 80 80 50 80 80 [% by weight]

Aluminum-

Aluminum aluminum aluminum aluminum aluminum aluminum aluminum aluminum

Aluminum-

Hexyl aluminum-aluminum Butyl-ethyl-butyl-ethyl-butyl-ethyl-butyl-ethyl-dibutyl-hexyl-

Addition - dibutyl-butyl-ethyl-ethyl-butyl-ethyl-butyl-ethyl phosphinate phosphinate phosphinate phosphinate phosphinate phosphinate phosphinate

phosphinate phosphinate phosphine phosphinate

ditto, lot

15.90 8.48 15.9 8.41 12.6 8.5 5.3 3.2 [wt%]

ditto, lot

53 53 53

[Ppm]

mixture

by mixing Mischu from

Al ₂ (HPO ₃ ) ₃ of basic * 4H ₂ 0 with aluminum Al ₂ (HPO ₃ ) ₃ Al ₂ (HP secondary aluminum secondary secondary heavy hydrogen secondary ^* 4H ₂ 0

Alkali ^* 4H ₂ 0

Aluminum aluminum phosphite Aluminum Al ₂ (HP0 ₃ ) ₃ Aluminum-soluble aluminum phosphites Aluminum-dried

Aluminum getroc and

Phosphates phosphorous Al (OH) phosphite ^* 4H ₂ 0 phosphite aluminum and hydrogen phosphite mixed phos- and

Sodium natrium Al ₂ (HPO ₃ ) ₃ (H ₂ PO ₃ ) 2 Al ₂ (HPO ₃ ) ₃ Al ₂ (HPO ₃ ) ₃ salts and aluminum phosphites

AI ₂ (HP0 ₃ ) ₃ phite

* 2H ₂ 0 nitrogen salts aluminum aluminum free phosphite phosp foreign ions example 80 Example dito, quantity

20 1 1 99 10 10 90 20 20 50 20 20 [% by weight]

Characteristics according to Pfrengle

Span of

ratio

0.67 0.48 0.39 0.5 0.48 0.39 0.5 0.48 0.35 0.5 0.39 0.35 radius / height

(= cot alpha)

Span of

Bulk cone20 12 9 13 12 9 13 12 8 13 9 8 height [mm]

Table 2: Flame retardant mixtures of Diethylphosphinsäuresalz, sulfate and aluminum phosphite

Example 16 17 18 19 20 21 22 23 24

Diethylphosphin¬

99 99 1 90 90 10 80 80 50 acid salt [wt.%]

Sodium alunite Basaluminit Sodium alunite Basalumini

Sodium sulfate Sodium sulfate Sodium sulfate Sodium sulfate Sodium sulfate

Addition of NaAl ₃ (SO ₄ ) ₂ Al ₄ (OH) ioS0 ₄ NaAl ₃ (SO ₄ ) ₂ Al ₄ (OH) i ₀ S

Na ₂ SO ₄ Na ₂ SO ₄ Na ₂ SO ₄ Na ₂ SO ₄ Na ₂ SO ₄

(OH) ₆ * 5H ₂ 0 (OH) e ^* 5H ₂ 0 ditto, amount [wt%] 7.4 7.4 7.4

ditto, amount [ppm] 13308 74 7874 242 7874 242

Mixture of

AI ₂ (HP0 ₃ ) ₃ ^*

basic 4H ₂ O with secondary aluminum secondary secondary aluminum-aluminum-aluminum-hydrogen-aluminum-aluminumAI ₂ (HP0 ₃ ) ₃ aluminum-aluminum-aluminum-aluminum

Aluminum phosphite phosphite soluble phosphites and hydrogen phosphite ^* 4H ₂ 0 phosphite phosphite mixed Al (OH) (H ₂ P0 ₃ ) ₂ aluminum aluminum phosphites

Al ₂ (HPO ₃ ) ₃ Al ₂ (HPO ₃ ) ₃ Al ₂ (HPO ₃ ) ₃ phosphites

* 2H ₂ 0 salts and salts

nitrogen-free

foreign ions

ditto, amount [% by weight] 1 1 99 10 10 90 20 20 50

Characteristics according to Pfrengle

Span of

ratio

0.5 0.42 0.5 0.5 0.42 0.56 0.48 0.42 0.5 radius / height

(= cot alpha)

Span of

Pouring cone height 13 10 13 13 10 15 12 10 13

[Mm]

Table 3: Flame retardant mixtures of Diethylphosphinsäuresalz, phosphate and aluminum phosphite

Example 25 26 27 28 29 30 31 32 33

Diethylphosphin¬

99 99 1 90 90 10 80 80 50 acid salt [wt.%]

Sodium aluminum, sodium aluminum

Aluminum aluminum aluminum aluminum aluminum aluminum dihydrogen dihydrogen dihydrogen dihydrogen

Addition phosphate phosphate phosphate phosphate phosphate

phosphate phosphate phosphate AIP0 ₄ AIPO4 AIPO4 AIPO4 AIPO4

NaH ₂ P0 ₄ (Al (H ₂ PO ₄ ) ₃ ) NaH ₂ PO ₄ (Al (H ₂ PO ₄ ) ditto, amount [% by weight] 6.4 6.4 6.4

ditto, amount [ppm] 8989 64 8843 56 8843 56

Mixture of

AI ₂ (HP0 ₃ ) ₃ ^*

basic 4H ₂ 0 with

secondary secondary aluminum secondary alkali AluminiumschwerAluminium- AluminiumAI ₂ (HP0 ₃₎ ₃ ^* Aluminiumhydrogen- AluminiumAluminium-

Aluminum phosphite phosphite soluble hydrogen phosphite 4H ₂ 0 phosphite phosphite and phosphite mixed Al (OH) (H ₂ P0 ₃ ) ₂ aluminum phosphites

Al ₂ (HPO ₃ ) 3 Al ₂ (HPO ₃ ) ₃ Al salts Al ₂ (HPO ₃ ) ₃ phosphites

* Salt 2H ₂ 0 and

nitrogen-free

foreign ions

ditto, amount [% by weight] 1 1 99 10 10 90 20 20 50

Characteristics according to Pfrengle

Span of

ratio

0.48 0.35 0.53 0.45 0.35 0.53 0.48 0.32 0.53 radius / height

(= cot alpha)

Span of

Pouring cone height 12 8 14 1 1 8 14 12 7 14

[Mm]

Table 4: flame retardant mixtures of Diethylphosphlnsäuresalz, Organylphosphonat and aluminum phosphite

Example 34 35 36 37 38 39 40 41 42

Diethylphosphln¬

99 99 1 90 90 10 80 80 50 acid salt [wt.%]

Aluminum aluminum aluminum aluminum aluminum disodium aluminum disodium aluminum aluminum aluminum ethyl ethyl ethyl ethyl ethyl phenyl ethyl ethyl phenyl

additive

phosphonate phosphonate phosphonate phosphonate phosphonate phosphonate phosphonate phosphona AI ₂ (EtPO ₃ ) ₃ Al ₂ (EtPO ₃ ) ₃ Al ₂ (EtPO ₃ ) ₃ Al ₂ (EtPO ₃ ) ₃ Na ₂ (EtPO ₃ ) Al ₂ (C ₆ H ₅ P0 ₃ ) ₃ Na ₂ (EtP0 ₃ ) Al ₂ (EtP0 ₃ ) ₃ Al ₂ (C ₆ H ₅ P dito, amount [wt%] 5.8 5.8 8

ditto, amount [ppm] 23330 58 9812 56 4666 29

Mixture of

AI ₂ (HP0 ₃ ) ₃ *

basic 4H ₂ O with aluminum secondary secondary secondary aluminum-aluminum-aluminum-hydrogen-aluminum-aluminumAl ₂ (HPO ₃ ) ₃ ^* aluminum-aluminum-aluminum

Aluminum phosphite phosphite soluble phosphites and hydrogen phosphite 4H ₂ 0 phosphite phosphite mixed phos- Al (OH) (H ₂ P0 ₃ ) 2 aluminum aluminum phosphites

Al ₂ (HPO ₃ ) ₃ Al ₂ (HPO ₃ ) ₃ Al ₂ (HPO ₃ ) ₃ phite

* 2H ₂ 0 salts and salts

nitrogen-free

foreign ions

ditto, amount [% by weight] 1 1 99 10 10 90 20 20 50

Characteristics according to Pfrengle

Span of

ratio

0.48 0.42 0.48 0.48 0.39 0.48 0.45 0.39 0.5 radius / height

(= cot alpha)

Span of

Cone cone height 12 10 12 12 9 12 1 1 9 13

[Mm]

Table 5: Flame retardant mixtures of Diethylphosphinsäuresalz, nitrate and aluminum phosphite

Example 43 44 45 46 47 48 49 50 51

Diethylphosphin¬

99 99 1 90 90 10 80 80 50 acid salt [wt.%]

basic alkaline

Aluminum aluminum aluminum aluminum sodium nitrate aluminum aluminum sodium nitrate aluminum

additive

Nitrate Al (N0 ₃ ) ₃ Nitrate Al (N0 ₃ ) ₃ Nitrate Al (N0 ₃ ) ₃ Nitrate Al (N0 ₃ ) ₃ NaN0 ₃ Nitrate Nitrate Al (N0 ₃ ) ₃ NaN0 ₃ Nitrate

Al (OH) (N0 ₃ ) ₂ Al (OH) (N0 ditto, amount [wt%] 5.7 5.7 6

ditto, quantity [ppm] 2405 57 2879 68 2879 68

Mixture of

AI ₂ (HP0 ₃ ) ₃ ^*

basic 4H ₂ O with aluminum secondary secondary aluminum-aluminum complex aluminum-aluminum-aluminum-aluminum-Al ₂ (HPO ₃ ) ₃ ^* aluminum-aluminum-aluminum

Aluminum phosphite phosphite soluble phosphites and hydrogen phosphite 4H ₂ 0 phosphite phosphite mixed Al (OH) (H ₂ P0 ₃ ) 2 aluminum aluminum phosphites

Al ₂ (HPO ₃ ) ₃ Al ₂ (HPO ₃ ) ₃ Al ₂ (HPO ₃ ) ₃ phosphites

* 2H ₂ 0 salts and salts

nitrogen-free

foreign ions

ditto, amount [wt .-%] 1 1 99 10 10 90 20 20 20

Characteristics according to Pfrengle

Span of

ratio

0.5 0.39 0.5 0.53 0.42 0.5 0.5 0.39 0.5 radius / height

(= cot alpha)

Span of

Pouring cone height 13 9 13 14 10 13 13 9 13

[Mm]

Table 6: Flame retardant mixtures of Diethylphosphinsäuresalz, chloride and aluminum phosphite

Example 52 53 54 55 56 57 58 59 60

Aluminum diethyl

99 99 1 90 90 10 80 80 50 phosphinate

basic alkaline

Aluminum-aluminum-aluminum-aluminum-sodium-aluminum-aluminum-sodium-aluminum

additive

Chloride AI (CI) ₃ chloride AI (CI) ₃ chloride AI (CI) ₃ chloride AI (CI) ₃ chloride NaCl chloride chloride AI (CI) ₃ chloride NaCl chloride

Al (OH) Cl ₂ Al (OH) Cl ₂ dito, Amount [wt%] 6.3 6.3 6.3

ditto, amount [ppm] 6268 63 2802 81, 0 2802 81

Mixture of

AI ₂ (HP0 ₃ ) ₃ ^*

basic 4H ₂ 0 with aluminum secondary secondary aluminum-aluminum-aluminum-hydrogen-aluminum-aluminum-aluminum-aluminum-AI ₂ (HPO ₃ ) ₃ * aluminum-aluminum-aluminum

Aluminum phosphite phosphite soluble phosphites and hydrogen phosphite 4H ₂ 0 phosphite phosphite mixed Al (OH) (H ₂ P0 ₃ ) ₂ aluminum aluminum phosphites

Al 2 (HPO ₃ ) ₃ Al ₂ (HPO ₃ ) ₃ Al ₂ (HPO ₃ ) ₃ phosphites

* 2H ₂ 0 salts and salts

nitrogen-free

foreign ions

same, amount [% by weight] 1 1 1 10 10 90 20 20 50

Characteristics according to Pfrengle

Span of

ratio

0.45 0.35 0.48 0.5 0.42 0.53 0.48 0.39 0.5 radius / height

(= cot alpha)

Span of

Pouring cone height 1 1 8 12 13 10 14 12 9 13

[Mm]

Table 7: Flame retardant mixtures of Diethylphosphinsäuresalz, acetate and aluminum phosphite

Example 61 62 63 64 65 66 67 68 69

Aluminum diethyl phosphinate 99 99 1 90 90 10 80 80 50

Addition aluminum aluminum aluminum aluminum aluminum sodium acetate basic aluminum sodium acetate basic

Acetate acetate acetate acetate NaCH ₃ C0 ₂ aluminum acetate NaCH ₃ C0 ₂ aluminum

Al (CH ₃ C0 ₂ ) 3 Al (CH ₃ C0 ₂ ) ₃ Al (CH ₃ C0 ₂ ) ₃ Al (CH ₃ C0 ₂ ) ₃ Acetate Al (OH) Al (CH ₃ C0 ₂ ) ₃ Acetate Al (O

(CH ₃ C0 ₂ ) ₂ (CH ₃ C0 ₂ ) ₂ ditto, amount [wt%] 5.8 5.8 5.8

ditto, amount [ppm] 8642 58 3890 69 3890 69

Aluminum phosphite basic secondary AI ₂ (HP0 ₃₎ ₃ * secondary mixture of aluminum secondary alkali aluminum AluminiumAluminium4H AluminiumAI ₂ 0 ₂ (HP0 ₃₎ ₃ * hydrogen- AluminiumAluminium- hydrogen- phosphite phosphite phosphite 4H ₂ 0 with phosphites and phosphite mixing phosphite AI (OH) (H ₂ PO ₃ ) ₂ Al ₂ (HPO ₃ ) ₃ Al ₂ (HPO ₃ ) ₃ heavy Al ₂ -Al ₂ (HPO ₃ ) ₃ phosphites

* 2H ₂ 0 soluble salts

Aluminum salts and

nitrogen-free

foreign ions

same, quantity [wt .-%] 1 1 99 10 99 90 20 20 50

Characteristics according to Pfrengle

Range of 0.5 0.48 0.53 0.5 0.48 0.53 0.5 0.42 0.48 ratio

Radius / height

(= cot alpha)

Range of 13 12 14 13 12 14 13 10 12

Poured cone height

[Mm]

Table 8: Composition of flame-retardant polymeric molding compounds and flame retardance tests of flame-retardant polymeric moldings according to UL 94

Polybutylene terephthalate: Celanex ^® 2500, Ticona Fa.

Polyamide 6.6: Ultramid ^® A3, BASF.

Polyamide 6: Zytel ^® 730, from Du Pont.

Polyamide 4.6: Stanyl ^® PA46, DSM company.

Fiberglass PBT: Vetrotex ^® EC 10983, from Saint-Gobain. Glass fibers PA: PPG 3540, PPG Industries, Inc

Glass fiber PA 46. Vetrotex ^® 995, from Saint-Gobain

Example 78

3 moles of Na ₂ HPO ₃ solution and 2 moles of Al ₂ (SO ₄ ) 3 solution are crystallized in aqueous solution at 150 ° C. and pH = 6.1 for 3 hours, filtered off and dried in air. The sodium aluminum phosphite becomes

X-ray examined by powder diffractometry. The stoichiometry is

Al _2, oNao, 6 (HPO ₃ ) ₂ , 89 ^* 0.28 H ₂ 0

Example 78:

X-ray powder data of sodium aluminum phosphite

Angle of reflex height

[° 2Th] [cts]

9,7557 297.79

12,6394 253,3

16,3439 2427,07

16.6964 1030.74

17.3912 580.89

18.7844 603.35

19.3678 650.66

23,7489 875.42

26.5675 1631, 28

26.9505 966.58

27,2826 1227.78

30,3357,943.17

30.8888 769.05

31, 9389 660.8 33.1695 1875.34

33.7547 556.79

34.1478 956.04

Example 79

3 moles of Na ₂ HPO ₃ solution and 2 moles of Al ₂ (SO ₄ ) 3 solution are crystallized in aqueous solution at 150 ° C. and pH = 3.5 for 3 hours, filtered off and dried in air.

Example 80

Example 81

3 mol of Na ₂ HPO ₃ solution and 2.01 mol of Al ₂ (SO) ₃ solution are crystallized in aqueous solution at 150 ° C. and pH = 2.5 for 3 hours, filtered off and dried in air.

Example 82

3 mol of Na ₂ HPO ₃ solution and 2.1 mol of Al ₂ (SO ₄ ) ₃ solution are brought to crystallization in aqueous solution at 150 ° C. and pH = 1 for 6 h, filtered off and dried in air.

Example 82:

X-ray powder data of Al ₂ (HPO

Angle [° 2Th] height [cts]

11, 7777 345, 54

13,6143 1270,15

14,7988 993,31 15,3862 494,47

16,2983 596,21

20,2051 1455.68

22.5312 1405.43

32,9021 1440.39

Examples 78 to 82:

X-ray powder data of mixtures of Al ₂ (HPO ₃ ) ₃ ^* 4H ₂ O and sodium aluminum phosphite

Example Height of the sodium-sodium reflex with aluminum content 9.7557 ° 2Th phosphite content

[cts] [wt%] [wt%]

78 297.79 100.0 4.1

79 152.76 51, 3 2.1

80 44.67 15.0 0.6

81 14.89 5.0 0.2

82 (Cf.) 0 0,0 0,0

Claims

claims

A halogen-free flame retardant mixture comprising 1 to 99 wt .-% of a component A and 1 to 99 wt .-% of a component B, wherein

Component A 85 to 99.995% by weight of a solid diethylphosphinic acid salt of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or contains a protonated nitrogen base and 0.005 to 15 wt .-% non-combustible additives and it is in the component B to

Aluminum phosphite acts.

2. Halogen-free flame retardant mixture according to claim 1, containing 20 to 80 wt.% Of component A and 20 to 80 wt .-% of component B.

3. Halogen-free flame retardant mixture according to claim 1 or 2, characterized in that the component A 92 to 99.9 wt .-%

Aluminiumdiethylphosphinsäuresalz and 0.5 to 8 wt .-% non-combustible

Contains additives.

4. Halogen-free flame retardant mixture according to one or more of claims 1 to 3, characterized in that it is at the additions to

Dialkylphosphinic salts of the formula (IV)

wherein R and R ^{2 are the} same or different and are independent

each other is ethyl, butyl, hexyl and / or octyl and M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated

Nitrogen base means with the proviso that R ¹ and R ^{2 are} not simultaneously ethyl; and / or that the additives are sulfates, phosphates, Phosphonates, nitrates, chlorides, sulfites and / or acetates, and that the sulfates, phosphates, phosphonates, nitrates, chlorides, sulfites and / or acetates are compounds containing cations of the alkali metals, the

Alkaline earth metals, the third main group, the subgroups of the

Periodic table and / or of protonated nitrogen bases.

5. Halogen-free flame retardants according to one or more of claims 1 to 4, characterized in that the dialkylphosphinic salts of the formula (IV) are ethyl-butylphosphinic acid salts, butyl-butylphosphinic acid salts, ethyl-hexylphosphinic acid salts, butyl

Hexylphosphinic salts and / or hexyl-hexylphosphinic salts.

6. Halogen-free flame retardant mixture according to one or more of claims 1 to 4, characterized in that the sulfates are sodium sulfates, sodium aluminum sulfates, alunites, aluminum sulfates, calcium sulfate, cerium sulphates, iron sulphates, potassium hydrogen sulphates, potassium sulphate, magnesium sulphates, manganese sulphates, monolithium sulphate, titanium sulphates, Zinc sulphate, tin sulphate,

Zirconium sulfates and / or their hydrates.

7. Halogen-free flame retardant mixture according to one or more of Claims 1 to 4, characterized in that the phosphates are aluminum phosphates, aluminum hydrogen phosphates, aluminum chloride phosphate, calcium hydrogen phosphates, calcium magnesium phosphates,

Magnesium hydrogenphosphates, potassium phosphates, potassium aluminum phosphate, potassium hydrogenphosphates, sodium hydrogenphosphates, sodium hydrate phosphates, sodium aluminum phosphates and / or their hydrates.

8. Halogen-free flame retardant mixture according to one or more of claims 1 to 4, characterized in that it is the phosphonates to mono-iCne-alkyl phosphonates, mono- (C ₆ -C ₀ -aryl) phosphonates and / or Mono (Ci-i 8-aralkyl) phosphonates; at the nitrates to aluminum nitrate,

Calcium nitrate, cerium nitrate, iron nitrates, potassium nitrate, lithium nitrate,

Magnesium nitrate, manganese nitrates, sodium nitrate, titanium nitrates, zinc nitrate, tin nitrates and / or zirconium nitrates and / or their hydrates; at the acetates

Aluminum acetate, calcium acetate, cerium acetate, iron acetate, lithium acetate,

Potassium acetate, sodium acetate, magnesium acetate, manganese acetate, titanium acetate, zinc acetate, tin acetate, zirconium acetate, aluminum chloride acetate,

Aluminiumhydrogenchloridacetat and / or their hydrate and the sulfites to potassium sulfites, potassium hydrogen sulfites, potassium metabisulfite, sodium sulfites,

Sodium metabisulfite, sodium hydrogen sulfites, ammonium sulfites and / or their hydrates.

9. Halogen-free flame retardant mixture according to one or more of claims 1 to 4, characterized in that the chlorides are aluminum chloride, calcium acetate chloride, calcium chloride, iron chloride,

Iron magnesium chloride, iron manganese chloride, iron zinc chloride, lithium chloride, magnesium chloride, titanium chloride, titanium oxide chloride, zinc chloride,

Zinc aluminum chloride, zinc oxide chloride, tin chloride, zirconyl chloride,

Aluminum chloride hydroxide, calcium hydroxide chloride, iron hydroxide chloride,

Lithium hydroxide chloride, magnesium hydroxide hydroxide, magnesium chloride hydroxide, zinc chloride hydroxide, stannous chloride, manganese chloride, potassium chloride,

Potassium aluminum chloride and / or their hydrates.

10. Halogen-free flame retardant mixture according to one or more of claims 1 to 9, characterized in that it is at the

Aluminum phosphites to those of the formulas (I), (II) and / or (III)

Al 2 (HPO ₃ ) 3 x (H ₂ O) _q (I) in the

q 0 to 4

means Al _2, ooM _z (HPO ₃ ) _y (OH) _v x (H ₂ O) _w (II) in the

M alkali metal ions

z 0.01 to 1.5

y is 2.63 to 3.5

v 0 to 2 and

w 0 to 4

means

Al2, oo (HPO3) u (H ₂ P0 ₃ ) tx (H ₂ O) _s (III) in the

u 2 to .2,99

t 2 to 0.01 and

s 0 to 4

means, and / or mixtures of aluminum phosphite of the formula (I) with

sparingly soluble aluminum salts and nitrogen-free foreign ions

Mixtures of aluminum phosphite of formula (III) with aluminum salts to give aluminum phosphite [Al (H2P0 ₃ ) ₃ ], aluminum secondary phosphite [Al ₂ (HPO ₃ ) ₃ ], aluminum phosphite [Al (OH) (H ₂ P0 ₃ ) ₂ ^* 2aq] to

Aluminum phosphite tetrahydrate [Al ₂ (HPO ₃ ) ₃ * 4aq] to give aluminum phosphonate, Al ₇ (HPO ₃ ) ₉ (OH) ₆ (1,6-hexanediamine) _{1, 5} ^* 12H ₂ O, Al ₂ (HPO ₃ ) ^{3 *} xAl ₂ O ₃ ^* nH ₂ 0 with x = 2.27-1, around Al ₄ H ₆ Pi ₆ Oi ₈ and / or around mixtures of 0-99.9% by weight

Al ₂ (HPO ₃ ) ₃ * nH ₂ O is 0.1-100% by weight sodium aluminum phosphite.

11. Halogen-free flame retardant mixture according to one or more of claims 1 to 10, characterized in that it is in the

Aluminum phosphite is a mixture of 50-99% by weight of Al ₂ (HPO ₃ ) ₃ × (H ₂ O) _q where q is 0-4 and 1-50% by weight of sodium aluminum phosphite.

12. Halogen-free flame retardant mixture according to one or more of claims 1 to 11, characterized in that it is in the

Aluminum phosphite around a mixture of 50-99% by weight Al ₂ (HPO ₃ ) ₃ × (H ₂ O) _q in which q is 0 to 4 and 1-50% by weight Al _2.0 oM _z (HPO ₃ ) y (OH) _v x (H ₂ O) _w (II) where M is sodium, z is 0.005 to 0.15, y is 2.8 to 3, 1, v is 0 to 0.4 and w is 0 to 4, is.

13. Halogen-free flame retardant mixture according to one or more of claims 1 to 12, characterized in that component A has an average particle size d50 of 0.05 to 10pm and component B has an average particle size d50 of 0.05 to 10μιη and a residual moisture content of 0 , 05 to

8 wt .-%.

14. A process for the preparation of a flame retardant mixture according to one or more of claims 1 to 13, characterized in that the

Components A and B are mixed together in powder form and

if necessary sieves.

15. Use of a halogen-free flame retardant mixture according to one or more of claims 1 to 14 as an intermediate for further

Syntheses, as a synergist, as a binder, as a crosslinker or accelerator in the curing of epoxy resins, polyurethanes, unsaturated polyester resins, as polymer stabilizers, as crop protection agents, as sequestering agents, as a mineral oil additive, as corrosion inhibitors, in detergents and

Detergent applications, in electronic applications, in or as

Flame retardant, as a flame retardant for clearcoats and

Intumescent coatings, in or as flame retardants for wood and other cellulosic products, in or as reactive and / or non-reactive

Flame retardant for polymers, for the production of flame-retardant

Polymer molding compounds, for the production of flame-retardant polymer moldings and / or for the flame-retardant finishing of polyester and cellulose pure and mixed fabrics by impregnation and / or as a synergist in further

Flame retardant mixtures.

16. flame-retardant thermoplastic or thermosetting

Polymer molding compound, polymer moldings, films, filaments and / or fibers, containing 0.1 to 45% by weight of halogen-free flame retardant mixture according to one or more of claims 1 to 13, 55 to 99.9% by weight

Reinforcement materials, wherein the sum of the components is 100 wt .-%.

17. flame retardant thermoplastic or thermosetting

Polymer molding composition, polymer moldings, films, filaments and / or fibers, containing 1 to 30 wt .-% halogen-free flame retardant mixture according to one or more of claims 1 to 13, 10 to 97 wt .-% thermoplastic or thermosetting polymer or mixtures the same, 1 to 30 wt .-% of additives and 1 to 30 wt .-% filler or reinforcing materials, wherein the sum of the components is 100 wt .-%.

18. Flame retardant thermoplastic or thermoset

Polymer molding composition, polymer moldings, films, filaments and / or fibers, comprising a halogen-free flame retardant mixture according to one or more of claims 1 to 13, characterized in that the polymer is thermoplastic polymers of the type polystyrene-HI (High Impact), polyphenylene ethers, polyamides, polyesters, polycarbonates and blends or

Polymer blends of the type ABS (acrylonitrile-butadiene-styrene) or PC / ABS

(Polycarbonate / acrylonitrile-butadiene-styrene) or PPE / HIPS

(Polyphenylene ether / polystyrene Hl) plastics and / or thermosetting

Polymers of the type unsaturated polyester or epoxy resins is.

19. Flame retardant thermoplastic or thermoset

Polymer molding compound, polymer molding, films, threads and / or fibers according to one or more of Claims 16 to 18, characterized in that the polymer is polyamide 4/6 (poly (tetramethylene-adipamide), (tetramethylene adipamide) to polyamide 6 (polycaprolactam, poly-6-aminohexanoic acid), to polyamide 6/6 ((poly (N, N'-hexamethyleneeadipinediamide) and / or to HTN (high temperature nylon).