WO2014060004A1 - Method for producing metal-2-hydroxydiphenyl-2'-(thio)phosphinates and metal-diphenylene-(thio)phosphonates, compositions containing same and use thereof as flame-proofing agents - Google Patents

Abstract

The invention relates to a method for producing metal-2-hydroxydiphenyl-2'-(thio)phosphinates of formula (I), proceeding from (6H)-dibenzo(c,e)(1,2)-oxaphosphorine-6-one(thione) (II) and metal (hydr)oxides or (basic) metal carbonates, and metal (thio)phosphonates (III) produced therefrom by cyclisation, wherein Mt = Cu, Ca, Mg, Zn, Mn, Fe, AI, Co, Ni, Sn, Zr, TiO, ZrO, Ce, MoO, WO₂, VO, B, Si, La, Ti, Bi or Sb X = H or OH, Y = O or S and n = 2 or 3, and compositions of same, and use of said compositions as flame-proofing agents for polymers, papers, textiles or wood plastic composites (WPC).

Description

Process for the preparation of metal 2-hydroxydiphenyl-2 ^' - (thio) phosphinates and metal diphenylene (thio) phosphonates, compositions containing them and their use as flame retardants

The invention relates to a process for the preparation of metal (thio) phosphinates starting from (6H) -dibenz (c, e) (1,2) -oxaphosphorin-6-one / thione (oxide / sulfide) or from 10-hydroxy- 9,10-Dihydro-9-oxa-phosphaphenanthrene-10-oxide (on) or of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-sulfide / (thione) and

Metal (hydr) oxides or (basic) metal carbonates, and optionally from cyclization produced metal (thio) phosphonates, compositions containing these compounds and the use of these compositions as flame retardants for polymers, paper, textiles or wood plastic composites (WPC).

Background and technical problem of the invention

9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (6H-dibenz [c, e] [1,2] oxaphosphorine-6-oxide) and its polymeric derivatives are indeed flame retardants in certain polyesters However, it has been shown that many plastics after addition of 9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide (6H-dibenz [c, e] [1, 2] oxa-phosphorin-6 oxide) or polymeric derivatives thereof are not readily processable or metered and necessary for processing

Glue machines together.

9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (6H-dibenz [c, e] [1,2] oxa-phosphorine-6-oxide) derivatives based on metal salts can remedy this situation. Salts of diorganylphosphinic acids, in particular their alkali metal and alkaline earth metal salts, and their use as flame retardants for polyesters and polyamides are known, for example, from DE 225 2258 and DE 244 7727. Mixtures of these salts with nitrogen bases and their use as effective flame retardants are described, for example, in WO 97/39053. Also known from US 4,208,321 are (poly) metal phosphinates of the metals Cu, Fe, Sn, Co, W, Mn, Cr, V, Ti, Zn, Cd and Mo, which are used as flame retardants for polyamides and polyesters. Again, these are the salts of

Diorganylphosphinic acids, especially since the Monoorganylphosphinsäuresalze, such as the salts of phenylphosphinic acid, which still have a P-H bond, are expressly referred to as disadvantageous, because they because of their light

Oxidability are unstable and thereby lose their flame retardancy over time.

JP 2001-139586 discloses the use of the zinc and aluminum salts of 10-hydroxy-9,0-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as flame retardants for organic polymers. The synthesis of these two salts takes place by double reaction starting from sodium phosphonate and metal chloride or metal sulfate. However, precipitates difficult to filter are obtained, which also have a high residual chloride content. The process is also not environmentally friendly because wastewater ballast must be disposed of with a high salt load. In addition, the starting phosphonic acid is only by oxidation with

concentrated peroxide solution accessible.

The zinc salt is also obtainable by reacting zinc acetate (hydrate) in ethanol and 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (JP 53127484). This process is uneconomical, since the alcohol

be recovered and the resulting acetic acid must be neutralized in the wastewater to the acetate.

The synthesis of zinc and aluminum salt of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is also published in DE 301 0375. The disadvantage here is the use of large amounts of organic solvents. The process is therefore not sustainable.

JP2003-306585 describes magnesium-bis-2-hydroxydiphenyl-2 phosphinate ^'and the Mg-salt of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as nucleating agents for polypropylene. A use as a flame retardant is not published. JP07-330963 describes the same salts as transparency improver for

Polypropylene. A use as a flame retardant is not published.

JP04-252245 describes barium bis (1'-hydroxy-2,2'-biphenylenephosphinate) in combination with inorganic fillers for use in polyolefins for improving the mechanical properties. A use as

Flame retardant is also not published.

JP03-223354 also describes zinc bis (1'-hydroxy-2,2'-biphenylene phosphinate) in combination with inorganic fillers for the improvement of

mechanical properties in polyolefins. A use as

Flame retardant is not published.

Furthermore, EP 1 657 972 A1 discloses a reaction product which is obtained by double reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (6H-dibenz [c, e] [1, 2] oxa phosphoric-6-oxide) with NaOH / H ₂ O with ZnC ^. The precipitation product thus obtained has the composition of zinc-bis-2-hydroxydiphenyl-2 ^'- phosphinate. A homologous aluminum salt is also exemplified in this document. It is prepared anhydrous in isopropanol from aluminum alcoholate and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (6H-dibenz [c, e] [1,2] oxa-phosphorin-6-oxide). Both syntheses are thus not sustainable.

This patent also discloses a combination of melamine polyphosphate and melamine cyanurate, respectively, prepared by the method described above

Zinc phosphinate described in relation to the burning behavior of polyamide.

DE 10 2010 026 973 A1 describes a flame retardant combination which determines the degradation reaction of plastics and the corrosion behavior during the

Should reduce processing. This can be done by adding metal oxides or

Metal hydroxides happen. It is also known that combinations of

Melaminpolyphosphat and Metallphosphinaten when processed in polyamide and polyester at higher temperatures to partial polymer degradation and

Polymer discoloration can lead (DE 10 2011 011 928). In addition, pure 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is known to be inadequate Thermostability (Phosphorus, Sulfur and Silicon, Vol. 139, 45-55)

Based on the above findings, it was therefore necessary to have an environmentally friendly, simple and resource-saving access to the claimed

open thermostable, phosphinate or phosphonate metal salts, wherein an aqueous reaction medium would be optimal and thus a handling of organic solvents is avoidable.

Description of the invention

Process for the preparation of metal phosphinates

It has surprisingly been found that a process for the preparation of metal (thio) phosphinates of the formula (I) and metal (thio) phosphonates of the formula (III), comprising the steps:

 (a) reacting (6H) -dibenzo (c, e) (1,2) -oxaphosphorin-6-one (thione) of the formula (II) with metal oxides, metal hydroxides or metal carbonates to form metal (thio) phosphinates of the formula (II) I), and

 (b) optionally reacting the metal (thio) phosphinates of the formula (I) from step (a) in a cyclization reaction for the preparation of

 Metal (thio) phosphonates of the formula (III),

wobei Mt ausgewählt ist aus Cu, Ca, Mg, Zn, Mn, Fe, AI, Co, Ni, Sn, TiO, Zr, ZrO, Ce, MoO, W0₂, VO, B, Si, La, Ti, Bi oder Sb; X = H oder OH, Y = O oder S und n = 2 oder 3 ist, o.g. Kriterien erfüllt.

wherein Mt is selected from Cu, Ca, Mg, Zn, Mn, Fe, Al, Co, Ni, Sn, TiO, Zr, ZrO, Ce, MoO, W0 ₂ , VO, B, Si, La, Ti, Bi or Sb; X = H or OH, Y = O or S and n = 2 or 3, above criteria met.

Preferably, in the formulas shown above, Mt is selected from Al, Ca, Cu, Mg, Zn or Zr. Particular preference is given to a process which uses metal metal oxides CaO, MgO, ZnO as starting materials and Ca (OH) ₂ , Mg (OH) ₂ , Zn (OH) ₂ and / or Al (OH) ₃ as metal hydroxides. ZnO and Ca (OH) ₂ and Mg (OH) ₂ are particularly preferred as starting materials.

Further, a method is preferred that uses as starting materials (basic) metal carbonate, in particular basic copper carbonate, basic magnesium carbonate, basic zinc carbonate, basic zirconium carbonate and basic aluminum carbonate. Particularly preferred starting materials are basic magnesium carbonate (hydromagnesite) and basic zinc carbonate (hydrozincite).

In principle, mixtures of two or more of the abovementioned compounds can also be used as starting materials.

The reaction in step (a) is preferably carried out in the aqueous phase, if appropriate in the presence of alcohols. Furthermore, step (a) is preferably carried out at a temperature of 20 to 90 ° C, more preferably at 30 to 70 ° C.

Particularly preferably, a granulation process can be followed by step (a). This may be preferred as spray agglomeration either in the spray dryer,

Spray granulator (top spray or bottom spray, countercurrent process),

Fluidized bed granulator or in a paddle mixer or horizontal dryer, wherein the introduced water is removed until the desired residual moisture is obtained. The granulation can take place by spray-drying an aqueous suspension of a metal (thio) phosphinate of the formula (I) at 70-80 ° C. or alternatively as spray granulation starting from a

Eduktmischung (fluidized bed) and spraying water onto the fluidized bed and subsequent drying can be obtained. The fluidized bed temperature is kept constant between 70-80 ° C, the granules dry at the same time and a free-flowing, non-dusting granules formed. The residual water content is approx. 0.5 - 1%.

The preparation of metal phosphonates (III) in step (b) is preferably anhydrous by thermal cyclization of metal (thio) phosphinates (I). This can be done in a mixer or dryer, electric oven, rotary kiln or in one High-speed mixer to be performed. Particularly preferably, the cyclization is carried out in a vertical or horizontal paddle mixer.

The cyclization is typically carried out at 130 to 270 ° C, preferably at 170 to 220 ° C and more preferably at 180 to 200 ° C.

Flame retardant compositions

The compounds obtained by the process described above are particularly suitable as flame retardants. Surprisingly, a flame retardant composition according to the invention has an improved flame retardancy in a variety compared to the individual components

various products, especially in their incorporation into plastics, and is easy to process in these plastics.

Preferably, synergistic compositions are used. These other components may be metal-containing or metal-free.

The present invention thus further relates to a composition comprising (i) a metal (thio) phosphonate of the formula (III), optionally in

 hio) phosphinate of the formula (I),

wherein Mt is selected from Cu, Ca, Mg, Zn, Mn, Fe, Al, Co, Ni, Sn, TiO, Zr, ZrO, Ce, MoO, W0 ₂ , VO, B, Si, La, Ti, Bi or Sb; Y = O or S and n = 2 or 3,

 and

 (ii-a) another metal-containing substance other than component (i)

 Component and / or

 (ii-b) a metal-free component or a melamine-metal phosphate.

Preference is given to compounds of the formula (III) where Y = S. The present invention thus further relates to metal thiophosphonates of the formula (III) wherein Mt is selected from Cu, Ca, Mg, Zn, Mn, Fe, Al, Co, Ni, Sn, TiO, Zr, ZrO, Ce, MoO, WO 2, VO, B, Si, La, Ti, Bi or Sb; Y = S and n = 2 or 3.

The synergistic components (ii-a) and (ii-b) of the composition according to the invention are shown below.

The other metal-containing component (ii-a) other than component (i) may in particular comprise metal hydroxide, metal phosphate, metal pyrophosphate, hydrotalcite, hydrocalumite, cationic or anionic modified organoclay, stannate salt or molybdate salt, metal borate or a metal phosphinate of formula (IV) .

wobei R und R² unabhängig voneinander Wasserstoff, lineares oder verzweigtes C C₆-Alkyl oder Phenyl sind, Mt¹ Ca, Mg, Zn oder AI ist und m = 2 oder 3 ist.

wherein R and R ^{2 are} independently hydrogen, linear or branched CC ₆ alkyl or phenyl, Mt ^{1 is} Ca, Mg, Zn or Al and m is 2 or 3.

Preference is given to melamine metal phosphates and azine metal phosphates.

Also preferred as component (ii-a) are melamine metal phosphates such as

for example, bis-melamine zinc diphosphate (M ₂ ZP ₂ ), bis-melamine magnesium diphosphate or bis-melamine aluminum triphosphate (M ₂ AP 3).

Particularly preferred as component (ii) are azine metal phosphates of the general formula [I],

[(A - H) ⁽⁺⁾ [M ^{m +} (PO ³ )] (Ρ ₂ 0 ₇ ) _ν ^{4 ψ * pH ₂ O] _z wherein (A - H) ^{(+) is} selected from melamine-H of the formula (1-1), melam-H of the formula (I-2), guanamine-H of the formula (I-3), wherein R = methyl or Phenyl is, and

(Amino) guanidine-H of the formula (I-4) wherein R = H or NH ₂ as shown in the following formula

wobei M ausgewählt ist aus Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, TiO, ZrO, VO, B, Si, AI, Sb, La, Ti, Zr, Ce, Bi oder Sn,

wherein M is selected from Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, TiO, ZrO, VO, B, Si, Al, Sb, La, Ti, Zr, Ce, Bi or Sn,

m is 2 or 3,

x and y are independently 0 or 1,

p is an integer from 0 to 4 and

z is an integer> 5,

where 1 + m = 3x + 4y

The preferred compounds hydrotalcite and hydrokalumite have, for example, the composition Mg ₆ Al ₂ (OH) i ₆ CO ₃ and Ca 1 OH ₂ CO ₃ . Organoclays are understood as meaning organophilically modified clay minerals (mainly montmorillonites) based on cation exchange, such as triethanol-tallow-ammonium-montmorillonite and triethanol-tallow-ammonium-hectorite, as described in Dr. med. G. Beyer; Conf. Fire Resistance in Plastics, 2007. Anionic organoclays are preferably organophil-modified hydrotalcites based on anion exchange with alkali metal roosinates, unsaturated and saturated fatty acid salts and long-chain alkyl-substituted sulfonates and sulfates.

Metal oxides are preferably selected from diantimony trioxide, diantimony tetroxide, diantimony pentoxide, zinc oxide or mixtures thereof. As the metal phosphate, metal pyrophosphates are preferred. Particularly preferred are aluminum and zinc pyrophosphate, zinc and aluminum triphosphate, aluminum and zinc metaphosphate, aluminum and zinc orthophosphate or mixtures thereof.

Among the cationically or anionically modified organoclays, the alkyl sulfate or fatty acid carboxylate-modified hydrotalcites or long-chain quaternary ammonium-modified clay minerals are particularly preferred.

Magnesium hydroxides (brucite) are preferred for the metal hydroxides,

Aluminum trihydroxide (ATH, gibbsite) or aluminum monohydroxide (boehmite) as well as hydromagnesite and hydrozincite. In addition to gibbsite and boehmite, the other modifications of aluminum hydroxides, namely bayerite, nordstrandite and diaspore are also mentioned.

Further preferred are with respect to molybdate salts or stannate salts

Ammonium heptamolybdate, ammonium octamolybdate, zinc stannate,

Zinkhydroxystannat or mixtures thereof These also act as

Rauchverminderer and thus have particularly advantageous properties in the flame retardants of the present invention.

From the class of metal borates alkali, alkaline earth or zinc borate are preferred. Also to be mentioned are aluminum borate, barium borate, calcium borate,

Magnesium borate, manganese borate, melamine borate, potassium borate, zinc borophosphate or mixtures thereof.

Metal phosphinates are preferably salts in which Mt is selected from Ca, Mg, Zn or Al. Preferred metal phosphinates are phenylphosphinate diethyl (methyl, ethyl) phosphinate, especially in combination with the aforementioned metals. Among the hypophosphites, the Mg, Ca, Zn and Al salts are particularly preferred.

The metal-free (co) component (component (ii-b) of the invention

Composition) includes in particular red phosphorus, oligomeric

Phosphate esters, oligomeric phosphonate esters, cyclic phosphonate esters,

Thiopyrophosphoric acid ester, melamine orthophosphate or melamine pyrophosphate, di- Melamine phosphate, melamine polyphosphate, melam (polyphosphate), and, Meiern and Diguanidinphosphat, Melaminphenylphosphinat, monomeric, oligomeric and polymeric Melaminphenylphosphonat, ammonium polyphosphate, melamine phenylphosphonate and its half ester salt, as in WO 2010/063623

described melaminebenzene phosphinate, as described in WO 2010/057851, hydroxyalkyl-phosphine oxides, as described in WO 2009/034023, tetrakis-hydroxymethyl-phosphonium salts and phospholane (oxide) - or phosphole derivatives and bisphosphoramidates with piperazine as a bridge member or a phosphinate ester, the substance class of NOR-HALS compounds (non-basic aminoether hindered amine light stabilizer) and mixtures thereof.

Preferred with respect to oligomeric phosphate esters are phosphate esters of formula (VI) or formula (VII),

wobei R jeweils unabhängig voneinander Wasserstoff, d-C₄-Alkyl oder Hydroxy ist, n = 1 bis 3 und o = 1 bis 10 ist. Besonders bevorzugt sind Oligomere mit R_n = H und Resorcin bzw. Hydrochinon als Bestandteil des Brückengliedes sowie R_n = H und Bisphenol-A oder Bisphenol-F als Bestandteil des Brückengliedes.

wherein each R is independently hydrogen, C 1 -C ₄ alkyl or hydroxy, n = 1 to 3 and o = 1 to 10. Particularly preferred are oligomers with R _n = H and resorcinol or hydroquinone as a constituent of the bridge member and R _n = H and bisphenol-A or bisphenol-F as a constituent of the bridge member.

Preference is given to oligomeric phosphonate esters of the formula (VIII)

(VIII) wobei R₃ Methyl oder Phenyl ist, x = 1 bis 20 ist, R jeweils unabhängig voneinander Wasserstoff, C C₄-Alkyl oder Hydroxy ist, n = 1 bis 3 und o = 1 bis 10 ist.

(VIII) wherein R _{3 is} methyl or phenyl, x = 1 to 20, each R is independently hydrogen, CC ₄ alkyl or hydroxy, n = 1 to 3 and o = 1 to 10.

Particularly preferred are oligomers with R _n = H and resorcinol or hydroquinone as part of the bridge member.

Further preferred are cyclic phosphonate esters of the formula (IX)

wobei y 0 oder 2 ist. Besonders bevorzugt ist Bis[5-ethyl-2-methyl-1 ,3,2- dioxaphosphorinan-5-at)methyl]methylphosphonat-P,P^'-dioxid.

where y is 0 or 2. Particularly preferred is bis [5-ethyl-2-methyl-1,3,2-dioxaphosphorinan-5-ate) methyl] methyl phosphonate P, P ^' dioxide.

Further preferred are thiopyrophosphoric acid esters of the formula (X):

Particularly preferred is ^2,2'-oxybis [5,5-dimethyl-1, 3,2-dioxaphosphorinane] 2,2 ^'- disulfide.

Of the hydroxyalkyl-phosphine oxides, preference is given to isobutyl-bis-hydroxymethyl-phosphine oxide and its combination with epoxy resins, as in WO-A

2009/034023 described.

Of the tetrakis-hydroxyalkyl phosphonium salts, the tetrakis-hydroxymethyl phosphonium salts are particularly preferred.

Of the phospholane derivatives or phosphol derivatives are

Dihydrophosphole (oxide) derivatives and phospholane (oxide) derivatives and their salts, as described in EP 1024 166, particularly preferred. Of the Bisphosphoramidaten the bis-di-ortho-xylylester are particularly preferred with piperazine as a bridge member.

Also particularly preferred are phosphinate esters, such as

Benzene monophenyl ester derivatives or phosphaphenanthrene derivatives, for example, 9,10-dihydro-9-0xa-10-phosphaphenanthrene-10-oxide or 6H-dibenzo (c, e) (1,2) -oxa-hosphorin-6-one) derivatives, such as shown in the following formulas.



Particular preference is given to compounds of the formulas (XI), (XII) or (XIII), as shown below.

Bis-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (6H-dibenz [c, e] [1,2] -oxa-phosphorine-6-oxide) compounds (Formula XIII), and 10 -Benzyl-9-oxa-10-phosphaphenanthrene-10-oxide, CAS-No: 1 13504-81 -7. The production of this

Connections is in Russ. J. Org. Chem. 2004, 40 (12), 1831-35. Other 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (β-H-dibenz [c, e] [1,2] oxa-phosphorin-6-oxide) derivatives useful in the present invention are described in U.S. Patent Nos. 4,136,066; US 8101678 B2 and US 8236881 B2.

Instead of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (6H-dibenz [c, e] [1,2] oxa-phosphorin-6-oxide), dihydro-oxa-phospha-anthracene can also be used oxide (on) can be used. An overview of this can be found in WO-A 2008/1 19693.

'= CH ₃ , nC ₄ H ₉ , or cC ₆ Hn

-C ₄ H ₉₎ or cC ₆ Hn

n = '= CH ₃ , nC ₄ H ₉ , or c-CeHn

 n = 2-10

with R '= CH ₃ , nC ₄ H ₉ , or cC ₆ Hn

Also preferred are polyols, aminouracils, POSS compounds, trishydroxyethyl isocyanurate, melamine cyanurate, expandable graphite or mixtures thereof. POSS compounds (polyhedral oligomeric silsesquioxanes) and their derivatives are described in more detail in POLYMER, Vol. 46, pp 7855-7866. Preferred are POSS derivatives based on methylsiloxane.

Furthermore, tris-hydroxyethyl isocyanurate polyterephthalates and

Triazine polymers having piperazine-1,4-diyl bridge members and morpholine-1-yl end groups may be included in the flame retardants of the present invention.

In addition, the following additives may be present in the flame retardants of the present invention: bis-azine pentaerythritol diphosphate salts, hexa-aryloxy triphosphazenes, polyaryloxy phosphazenes and siloxanes, for example of the general formula (R ₂ SiO) r or (RSiO-i, ₅ ) r.

[35948-24-4]: ^'- (hydroxy [1, ^1' -biphenyl] -2-at) -2-phosphinic acid CAS-No (metal salts of 2: Particularly preferred are the following individual components.

According to formula (I):

Mg (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) ₂ CAS number: [165597-56-8],

Zn (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) ₂ CAS number: [139005-99-5],

AI (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) ₃ CAS No. [145826-41 -1], Ca (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) ₂ According to formula (II):

Mg (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ CAS-No: [147025- 23-8],

Zn (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ CAS No: [69151 -14-0],

Al (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-at) ₃ CAS No: [121 166- 84-5].

Ca (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ CAS-No: [144722- 45-2],

In principle, mixtures of two or more of the compounds described above may also be present in the compositions of the present invention. Particularly preferred are the following combinations.

Dual combination: melamine cyanurate (MC) or melamine polyphosphate and

Mg (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

Zn (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

AI (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _3,

Mg (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ ,

Zn (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ or

 Al (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-at) 3;

MZP or MAP ₂ (melamine zinc phosphate / melamine aluminum diphosphate) and

Mg (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

Zn (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

AI (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _3,

Mg (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ ,

Zn (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ or

Al (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-at) ₃ ;

M ₂ ZP ₂ or M ₂ AP ₃ (Dimelamin-zinc diphosphate / Dimelamin-aluminum triphosphate) and Mg (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2, Zn (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

AI (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _3,

 Mg (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) 2,

Zn (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ or

Al (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₃

Triple combination: melamine cyanurate (MC) or melamine polyphosphate, and Mg (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

Zn (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

AI (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _3,

Mg (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ ,

Zn (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ or

Al (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₃

and zinc borate.

MZP or MAP ₂ (melamine zinc phosphate / melamine aluminum diphosphate) and

Mg (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

Zn (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

AI (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _3,

Mg (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ ,

Zn (O-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ or

Al (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₃

and zinc borate.

M ₂ ZP ₂ or M ₂ AP ₃ (dimelamine zinc diphosphate / dimelamine aluminum triphosphate) and

Mg (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

Zn (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

AI (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _3,

Mg (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ ,

Zn (O-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ or

Al (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₃

and zinc borate.

Melamine cyanurate (MC) or melamine polyphosphate and

Mg (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2, Zn (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) 2,

AI (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _3,

Mg (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ ,

Zn (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ or

Al (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₃

and zinc stannate.

MZP or MAP ₂ (melamine-zinc phosphate / melamine Aluminiumdiphosphat) and Mg (2 ^'-hydroxy [, ^1' -biphenyl-2-yl-2-phosphinate) _2,

Zn (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

AI (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _3,

Mg (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ ,

Zn (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ or

Al (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₃

and zinc stannate.

M ₂ ZP ₂ or M ₂ AP ₃ (Dimelamin-zinc diphosphate / Dimelamin-aluminum triphosphate) and Mg (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

Zn (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

AI (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _3,

Mg (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ ,

Zn (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ or

Al (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₃

and zinc stannate.

Melamine cyanurate (MC) or melamine polyphosphate and

Mg (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

Zn (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

AI (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _3,

Mg (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ ,

Zn (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ or

Al (O-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₃

and boehmite.

MZP or MAP ₂ (melamine zinc phosphate / melamine aluminum diphosphate) and Mg (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

Zn (2 ^'-hydroxy [, ^1' -biphenyl-2-yl-2-phosphinate) 2,

AI (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _3,

Mg (10-oxy-9, 0-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ ,

Zn (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ or

AI (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-at) 3

and boehmite.

M ₂ ZP ₂ or M ₂ AP ₃ (Dimelamin-zinc diphosphate / Dimelamin-Aluminiumtripho ^ and Mg (2 ^'-hydroxy [, ^1' -biphenyl-2-yl-2-phosphinate) _2,

Zn (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

AI (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _3,

Mg (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ ,

Zn (10-oxy-9, 0-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ or

Al (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₃

and boehmite.

MCP + MPP and

Mg (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

Zn (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

AI (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _3,

Mg (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ ,

Zn (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ or

Al (O-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₃ .

MAP ₂ + MPP and

Mg (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

Zn (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _2,

AI (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) _3,

Mg (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ ,

Zn (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₂ or

Al (10-oxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-oxide-ate) ₃ . Very particular preference is given to metal salts such as 10-hydroxy-9,10-dihydro-9-oxa-phosphaphenanthrene-10-sulfide CAS No .: [62839-09-2], Zn (10-oxy-9,10-dihydroxy) 9-oxa-10-phosphaphenanthrene-sulfide-at) _2, Al (10-oxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-oxide at) ₃ and Zn (2 ^'-hydroxy [1, 1 ^' Biphenyl-2-yl-2-phosphinate) 2

Use of the phosphinates according to the invention

A particular embodiment of the invention relates to the use of the compositions described above, which -phosphinates inventive metal-2-hydroxydiphenyl-2, ^'and the metal phosphonates prepared therefrom by cyclization contained in a polymer as a flame retardant. The present invention thus further relates to compositions, as described above, which additionally contain a polymer or a polymer mixture. Preferably, the composition described above comprising component (i), (ii-a) and / or (ii-b) is first prepared and this composition incorporated into the polymer or the polymer mixture.

The invention also relates to a process for the preparation of flame-retardant polymer molding compositions, characterized in that the stabilized flame retardants according to the invention are homogenized with the polymer granules and any additives in a compounding unit at higher temperatures in the polymer melt and then the homogenized polymer strand is withdrawn, cooled and portioned. The resulting granules are e.g. dried at 90 ° C in a convection oven.

The compounding unit preferably comes from the group of single-screw extruders, multizone screws or twin-screw extruders. suitable

Compounding units are single-screw extruders or single-screw extruders, e.g. the company Berstorff GmbH, Hannover and or the company Leistritz, Nuremberg,

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

Short-Compression Screws, Ko-Kneader eg Fa. Coperion Buss Compounding Systems, CH-Pratteln, eg MDK / E46-1 1 D and / or laboratory kneader (MDK 46 from Buss, Switzerland with L = 1 1 D); Twin-screw extruder, for example from the company Coperion Werner Pfleiderer GmbH & Co. KG, Stuttgart (ZSK 25, ZSk 30, ZSK 40, ZSK 58, ZSK MEGAcompounder 40, 50, 58, 70, 92, 1 19, 177, 250, 320, 350, 380) and / or the Berstorff GmbH, Hannover, Leistritz Extrusionstechnik GmbH, Nuremberg; Ring extruder eg from the company 3 + Extruder GmbH, running with a ring of three to twelve small screws, which rotate around a static core and / or

Planetary roller extruder e.g. Entex, Bochum and / or degassing extruders and / or cascade extruders and / or Maillefer screws; Compounder with counter-rotating twin screw e.g. Complex 37- or -70-types of the company Krauss-Maffei Berstorff.

The polymer is typically a thermoplastic, which is preferably selected from the group consisting of polyamide, polycarbonate, polyolefin, polystyrene, polyester, polyvinyl chloride, polyvinyl alcohol, ABS and polyurethane, or a

Duroplast is, which is preferably selected from the group consisting of epoxy resin (with hardener), phenolic resin and melamine resin.

It is also possible to use mixtures of two or more polymers, in particular thermosets and / or thermosets, in which the azine-metal phosphate according to the invention is used as flame retardant.

Examples of such polymers are:

Polymers of mono- and diolefins, e.g. Polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyvinylcyclohexane, polyisoprene or

Polybutadiene and polymers of cycloolefins, e.g. of cyclopentene or norbornene and polyethylene (also cross-linked), e.g. High Density Polyethylene (HDPE) or High Molecular Weight (HDPE-HMW), High Density Polyethylene with Ultra-High Molecular Weight (HDPE-UHMW), Medium Density Polyethylene (MDPE), Low Density Polyethylene (LDPE) and Linear Low Density Polyethylene ( LLDPE), (VLDPE) and (ULDPE) as well as copolymers of ethylene and vinyl acetate (EVA);

 Polystyrenes, poly (p-methylstyrene), poly (α-methylstyrene);

 Copolymers and graft copolymers of polybutadiene-styrene or

Polybutadiene and (meth) acrylonitrile such as ABS and MBS; Halogen-containing polymers, for example polychloroprene, polyvinyl chloride (PVC);

Polyvinylidene chloride (PVDC), copolymers of vinyl chloride / vinylidene chloride,

Vinyl chloride / vinyl acetate or vinyl chloride / vinyl acetate.

 Poly (meth) acrylates, polymethyl methacrylates (PMMA), polyacrylamide and polyacrylonitrile (PAN).

 Polymers of unsaturated alcohols and amines or their Azylderivaten or acetals, such. Polyvinyl alcohol (PVA), polyvinyl acetates, stearates, benzoates or maleates, polyvinyl butyral, polyallyl phthalates and polyallyl melamines;

 Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxides, polypropylene oxides and their copolymers with bisglycidyl ethers;

 Polyacetals, such as polyoxymethylene (POM) and polyurethane and acrylate modified polyacetals;

 Polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides;

 Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, e.g. Polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 12/12, polyamide 11, polyamide 12, aromatic polyamides derived from m-xylylenediamine and adipic acid and copolyamides modified with EPDM or ABS. Examples of polyamides and

Copolyamides are derived from ε-caprolactam, adipic acid, sebacic acid, dodecanoic acid, isophthalic acid, terephthalic acid, hexamethylenediamine,

Tetramethylenediamine, 2-methyl-pentamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, m-xylylenediamine or bis (3-methyl-4-aminocyclohexyl) methane;

 Polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.

 Polyester derived from dicarboxylic acids and dialcohols and / or

Hydroxycarboxylic acids or the corresponding lactones, e.g.

Polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylcyclohexane terephthalate, polyalkylene naphthalate (PAN) and

Polyhydroxybenzoates, polylactic acid esters and polyglycolic acid esters;

 Polycarbonates and polyestercarbonates;

polyketones; Mixtures or alloys of above-mentioned polymers, eg PP / EPDM, PA / EPDM or ABS, PVC / EVA, PVC / ABS, PBC / MBS, PC / ABS, PBTP / ABS, PC / AS, PC / PBT, PVC / CPE, PVC / Acrylate, POM / Thermoplastic PUR, PC / Thermoplastic PUR, POM / Acrylate, POM / MBS, PPO / HIPS, PPO / PA6.6 and Copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC, as well as TPE-O, TPE-S and TPE-E;

 Thermosets such as PF, MF or UF or mixtures thereof;

 Epoxy resins - thermoplastics and thermosets;

 Phenol resins;

 Wood-plastic composites (WPC) as well as polymers based on PLA, PHB and starch.

Preference is given to PA, PET, PBT, PUR, PC and epoxy resins. Particularly preferred are glass fiber reinforced PA and PBT.

The concentration of the flame retardant preparations according to the invention, consisting of metal (thio) phosphinate or metal (thio) phosphonate (i) and the additional metal-containing component (ii-a) and / or the metal-free component (ii-b) is preferably in a polymer or a polymer mixture 0.1 to 60 wt .-%, based on the polymer or the polymer mixture. The

Component ratio in the composition consisting of component (i) to the co-components (ii-a) and / or (ii-b) is preferably in the range of 1: 1 to 1: 4.

According to a preferred embodiment of the invention, the

Polymer material according to the invention further contain fillers, which are preferably selected from the group consisting of metal hydroxides and / or

Metal oxides, preferably alkaline earth metal hydroxides, for example

Magnesium hydroxide, aluminum hydroxide, silicates, preferably phyllosilicates, such as bentonite, kaolinite, muscovite, pyrophyllite, marcasite, and talc or others

Minerals such as wollastonite, silica such as quartz, mica, feldspar and titanium dioxide, alkaline earth metal silicates and alkali metal silicates, carbonates,

preferably calcium carbonate and talc, clay, mica, silica, calcium sulfate, barium sulfate, pyrite, glass fiber, glass beads, glass particles and glass beads, wood flour, cellulose powder, carbon black, graphite, chalk and pigments. These fillers can impart further desired properties to the polymer material of the invention. In particular, for example, by a

Reinforced with glass fibers, the mechanical stability can be increased or dyed by adding dyes to the plastic.

According to a further embodiment, the polymer materials may contain further additives, such as antioxidants, light stabilizers, process auxiliaries,

Nucleating agents, antistatic agents, lubricants, such as calcium and zinc stearate,

Viscosity improvers, impact modifiers and in particular compatibilizers and dispersants.

In addition, foaming agents can be added to the polymer in addition to the azine metal phosphate of the present invention. Foaming agents are preferably melamine, melamine-formaldehyde resins, urea derivatives such as urea, thiourea, guanamine, benzoguanamine, acetoguanamine and succinylguanamine, dicyandiamide, guanidine and guanidine sulfamate and also other guanidine salts or allantoins and glycolurils.

In addition, a polymer containing the azine metal phosphate according to the invention may also comprise antidripping agents, in particular

Polytetrafluoroethylene base, included. The concentration of such anti-dripping agents is preferably 0.01 to 15 wt .-%, based on the processed

Polymer.

Examples

The following examples serve to further illustrate the invention.

Comparative Example 1 (according to EP 1 657 972, Example 1)

Preparation of zinc bis-2-hydroxybiphenyl-2 ^'phosphinate (C ₂₄ H ₂ o0 ₆ P ₂ Zn), starting from ZnCl ₂ and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (C ₁₂ H ₉ 0 ₂ P): 43.24 g (0.2 mol) of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide were suspended in 500 ml of water with stirring. Then 16.0 g (0.2 mol, 50% solution) of NaOH are added, resulting in a clear solution. To this is added dropwise 13.6 g (0.1 mol) of zinc chloride dissolved in water. The mixture was then stirred for a further 2h, the resulting white precipitate was filtered off, washed with water and dried at 1 10 ° C constant weight. Yield: 50.5 g (95.0% of theory) pH: 5.6 (10% suspension in distilled water, subsequent centrifugation;

measured with a calibrated pH meter)

 Conductivity: 2100 S / cm (10% suspension in distilled water, subsequent centrifugation, measured with a calibrated conductometer)

Example 2:

Preparation of zinc bis-2-hydroxybiphenyl-2 ^'phosphinate (C ₂₄ H ₂ oO ₆ P ₂ Zn) based on basic zinc carbonate (hydrozincite) Zn ₅ (OH) 6 (CO ₃₎ 2, and 9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide (Ci ₂ HgO ₂ P):

432.4 g (2.0 mol) of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-0-oxide (granules: 200-400μιτι) were suspended in 3000 ml of water with stirring. To this

1 15.3 g (0.21 mol) of basic zinc carbonate was added in portions to the suspension. After stirring for 1 hour at 80 ° C, a voluminous precipitate formed under CO ₂ evolution. The mixture was then stirred for a further 2 h (until disappearance of the melting point peak in the DSC), cooled to room temperature, the resulting white precipitate was filtered off with suction, washed with water and dried at 1 10 ° C constant weight. Yield: 480 g (90.0% of theory, mp> 300 ° C.) pH: 5.6 (10% suspension in distilled water, subsequent centrifugation;

measured with a calibrated pH meter)

Conductivity: 453 S / cm (10% suspension in distilled water, following

centrifugation; measured with a calibrated conductometer) Elemental analysis: found: C = 54.40%; H = 3.45%; P = 1 1, 45%; Zn = 12.10%

 calculated: C = 54.16%; H = 3.76%; P = 1 1, 66%; Zn = 12,30%

The comparison with Example 1 shows that the conductivity of the product according to the invention is lower by a factor of 4.7 and is therefore more suitable in electronic applications.

Example 3A:

Preparation of zinc bis-2-hydroxybiphenyl-2 ^'phosphinate (C ₂₄ H ₂ o0 ₆ P ₂ Zn), starting from zinc oxide (ZnO) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide ( C ₁₂ H ₉ O ₂ P):

216.2 g (1, 0 mol) of 9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide were suspended in 2000 ml of water with stirring. To this suspension were 41, 9g

(0.51 mol) ZnO added in portions. After 1 hour of stirring at 80 ° C, a voluminous precipitate formed. The mixture was then stirred for 2 h (until disappearance of the melting point peak in the DSC), cooled to room temperature, the resulting white precipitate was filtered off, washed with water

washed and dried at 1 10 ° C constant weight. Yield: 255.0 g (96.0% of theory) pH: 5.5 (10% suspension in distilled water, subsequent centrifugation;

measured with a calibrated pH meter)

Conductivity: 380pS / cm (10% suspension in distilled water, following

centrifugation; measured with a calibrated conductometer)

Elemental analysis: found: C = 53.90%; H = 3.50%; P = 11, 75%; Zn = 12.45% calculated: C = 54.16%; H = 3.76%; P = 11, 66%; Zn = 12,30%

The comparison with Example 1 shows that the conductivity of the product according to the invention is lower by a factor of 5.5 and is therefore more suitable in electronic applications. Example 3B: Spray Method

The drying can be carried out by spraying. In this case, the nutschfeuchte filter cake is suspended in water and the resulting slurry dried by spray granulation at 70-80 ° C.

Example 4:

Preparation of magnesium bis-2-hydroxybiphenyl-2 ^'phosphinate (C ₂₄ H ₂ o06P ₂ Mg), starting from basic magnesium carbonate (hydromagnesite) ₅ Mg (OH) ₂ (C0 _{3) 4} * 4H ₂ 0 9,10 Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (Ci ₂ H ₉ O ₂ P):

43.24 g (0.2 mol) of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was suspended in 400 ml of water with stirring. To this suspension were 9.8g

(0.021 mol) of hydromagnesite added in portions. The further procedure was carried out as in Example 2. Yield: 480 g (90.0% of theory, mp> 300 ° C.) pH: 6.6 (10% suspension in distilled water, subsequent centrifugation;

measured with a calibrated pH meter)

Example 5:

Preparation of calcium bis-2-hydroxybiphenyl-2 ^'phosphinate (C ₂₄ H ₂ o06P2Ca) starting from calcium hydroxide and 9,10-dihydro-9-oxa-10-phosphaphenanthren- 10-oxide (C ₂ H ₉ 0 ₂ P ):

43.24 g (0.2 mol) of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was suspended in 400 ml of water with stirring. To this suspension was 7.4g

(0.1 mol) of calcium hydroxide added in portions. The further procedure was carried out as in Example 2. Yield: 49.0 g (97.0% of theory, mp> 300 ° C.) pH: 6.6 (10% suspension in distilled water, subsequent centrifugation;

measured with a calibrated pH meter)

Example 7:

Preparation of zinc salt of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (C ₂₄ H ₆ O ₆ P ₂ Zn) starting from zinc oxide and 10-hydroxy-9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (Ci ₂ H ₉ 0 ₃ P): 46.4 (0.2 mol) of 10-hydroxy-9,10-dihydro-9-oxa-O-phosphaphenanthrene-10-oxide was suspended in 400 ml of water with stirring. To this suspension was added portionwise 8.4 g (0.11 mol) of zinc oxide. The further procedure was carried out as described in Example 3. Yield: 52.0 g (98.5% of theory, mp> 300 ° C.) pH: 5.9 (10% suspension in distilled water, subsequent centrifugation;

measured with a calibrated pH meter)

Conductivity: 390 S / cm (10% suspension in distilled water, following

centrifugation; measured with a calibrated conductometer)

Elemental analysis: found: C = 54.80%; H = 3.50%; P = 11, 40%; Zn = 2.50%

 calculated: C = 54.62%; H = 3.05%; P = 1, 73%; Zn = 12.39%

Example 8 and Example 9:

Magnesium and calcium salts of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide were prepared similarly as in Example 7, but starting from magnesium hydroxide or calcium hydroxide (mp> 300 ° C ).

Example 11:

Preparation of zinc salt of 0-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-sulphide (C ₂₄ H- | ₆ O ₄ P ₂ S ₂ Zn) starting from zinc oxide and 10-hydroxy 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-sulphide (Ci ₂ H ₉ O ₂ PS):

49.6 (0.2 mol) of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-sulfide were suspended in 400 ml of water with stirring. Subsequently, 16.0 g (50% solution, 0.2 mol) of NaOH are added, resulting in a clear solution. 13.6 g (0.1 mol) of ZnCl ₂ dissolved in water are added dropwise to this dropwise solution, followed by stirring for about 1 h. The resulting white precipitate was filtered off, washed with water and dried at 110 ° C constant weight. Yield: 42.5 g (76.0% of theory) mp: 258-261 ° C Example 12:

Preparation of zinc salt of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (C ₂₄ Hi ₆ O ₆ P2 n) starting from zinc bis-2-hydroxybiphenyl-2 ^' - phosphinate (C ₂₄ H ₂₀ O ₆ P2Zn) by thermal cyclization:

350g zinc bis-2-hydroxybiphenyl-2 ^'phosphinate (C ₂ H ₂ o0 ₆ P2Zn) were annealed at 220 ° C for 90 min.. Upon cooling, a white-beige powder resulted. Yield: 347g (quantitative). pH: 5.9 (10% suspension in distilled water, subsequent centrifugation;

measured with a calibrated pH meter)

Conductivity: 370pS / cm (10% suspension in distilled water, following

centrifugation; measured with a calibrated conductometer)

The products thus obtained were investigated thermoanalytically (TGA and DSC). The TGA results are summarized in Tab.

Tab. 1: Thermogravimetric analysis: weight loss

From Table 1 it can be seen that due to the TGA data all compounds are suitable as flame retardants (components). For further Ausprüfungen the product was (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) ₂ Zn (Example 3)

selected. The effect is demonstrated in Example 13. Example 13: (Use as flame retardant in PA)

Materials: PA 6.6 (Durethan A30S, LANXESS); Glass fiber (Thermo Flow ^® 671; 10 mx4mm; Fa John Manville.); MPP melamine polyphosphate (Melapur 200; BASF.), (2 ^'-hydroxy [1, ^1' -biphenyl-2-yl-2-phosphinate) ₂ Zn (Example 3), Dimelamin- zinc diphosphate (own product).

The components were compounded on a Leistritz ZSE 27HP-44D (0 = 27 mm, 44 D), twin screw extruder and granulated. From these granules standardized test specimens (d = 1, 6mm) were produced by injection molding. The fire test was performed according to UL-94 test. The results are summarized in Tab.

Tab. 2: Flame retardancy test

Claims

claims: 1 . Process for the preparation of metal (thio) phosphinates of the formula (I) and metal (thio) phosphonates of the formula (III), comprising the steps: (a) reacting (6H) -dibenz (c, e) (1,2) -oxaphosphorin-6-one / thione (oxide / sulfide) of formula (II), or of 10-hydroxy-9,10-dihydro -9-oxa-10-phosphaphenanthren-10-oxide (on) of the formula (II), or of 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthren-10-sulfide (thione) of the formula (II), with metal oxides, metal hydroxides, basic metal carbonates or metal carbonates To obtain metal (thio) phosphinates of the formula (I), and (b) optionally reacting the metal phosphinates of step (a) in a cyclization reaction to produce metal (thio) phosphonates of the formula (III),

wherein Mt is selected from Cu, Ca, Mg, Zn, Mn, Fe, Al, Co, Ni, Sn, TiO, Zr, ZrO, Ce, MoO, WO ₂ , VO, B, Si, La, Ti, Bi or Sb; X = H or OH, Y = O or S and n = 2 or 3. 2. The method according to claim 1, characterized in that Mt is selected from Al, Ca, Ce, Mg, Sn, Zn and Zr. 3. The method according to claim 1 or 2, characterized in that the Compound of formula (II) is reacted with a metal oxide, a metal hydroxide or a basic metal carbonate. 4. The method according to any one of the preceding claims, characterized in that step (a) takes place in an aqueous phase or in a 9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide - melt. 5. The method according to any one of the preceding claims, characterized in that the reaction in step (a) takes place at 20 to 90 ° C, preferably 30 to 70 ° C. 6. The method according to any one of the preceding claims, characterized in that the compounds of the formula (I) are obtained by spray drying or spray granulation. 7. The method according to any one of the preceding claims, characterized in that the reaction in step (b) takes place in an anhydrous medium by thermal cyclization of compounds of the formula (I). 8. The method according to claim 7, characterized in that the thermal cyclization at a temperature of 130 to 270 ° C, preferably at 170 to 220 ° C, more preferably at 80 to 200 ° C, takes place. 9. Composition comprising  (i) a metal (thio) phosphonate of the formula (III), optionally in  hio) phosphinate of the formula (I),

wherein Mt is selected from Cu, Ca, Mg, Zn, Mn, Fe, Al, Co, Ni, Sn, TiO, Zr, ZrO, Ce, MoO, W0 ₂ , VO, B, Si, La, Ti, Bi or Sb; Y = O or S and n = 2 or 3,  and  (ii-a) another metal-containing substance other than component (i)  Component and / or (ii-b) a metal-free component or a melamine-metal phosphate. 10. The composition according to claim 9, characterized in that the metal-containing component (ii-a) is selected from metal hydroxide, metal phosphate, metal pyrophosphate, hydrotalcite, hydrocalumite, zeolite, preferably zeolite X or zeolite Y, cationic or anionic modified organoclay, stannate salt or molybdate salt, metal borate, metal phosphinate of the formula (IV) or mixtures thereof,

wherein R ¹ and R ^{2 are} independently hydrogen, linear or branched Cr C ₆ alkyl or phenyl, Mt is selected from Ca, Mg, Zn or Al and m = 2 or 3. 1 1. A composition according to claim 10, characterized in that the metal hydroxide is selected from magnesium hydroxide (brucite), aluminum trihydroxide (ATH, gibbsite), aluminum monohydroxide (boehmite) or mixtures thereof. 12. The composition according to claim 10, characterized in that the molybdate salt or stannate salt is selected from ammonium heptamolybdate, ammonium octamolybdate, zinc stannate, zinc hydroxystannate or mixtures thereof. 13. The composition according to claim 10, characterized in that the metal borate is selected from alkali metal borate, alkaline earth borate, zinc borate or mixtures thereof. 14. The composition according to claim 10, characterized in that the metal phosphinate of the formula (IV) is selected from hypophosphite, Phenylphosphinate, diethyl (methyl, ethyl) phosphinate or mixtures thereof. 15. A composition according to any one of claims 9 to 14, characterized in that Mt in the metal phosphinate (I) and / or in the metal phosphonate (III) is selected from Al, Ca, Ce, Mg, Sn, Zn and Zr. 16. A composition according to any one of claims 9 to 15, characterized in that the metal-free component (ii-b) is selected from red phosphorus, oligomeric phosphate ester, oligomeric phosphonate ester, cyclic phosphonate ester, thiopyrophosphoric acid ester, ammonium polyphosphate, Hydroxyalkylphosphine oxide, tetrakis-hydroxyalkylphosphonium salt, Phospholane (oxide) derivative, dihydrophosphole (oxide) derivative, phosphinate ester, Melamine polyphosphate, melamine orthophosphate, melamine pyrophosphate, Melaminphenylphosphinat, (monomeric, oligomeric, polymeric) Melaminphenyl- phosphonate, melam, Meiern or mixtures thereof. 17. A composition according to claim 9, characterized in that the melamine metal phosphate of component (ii-b) is selected from melamine zinc phosphate, melamine magnesium phosphate, melamine aluminum pyrophosphate, bis-melamine zinc diphosphate, bis-melamine magnesium diphosphate, bis- Melamine aluminum triphosphate or mixtures thereof. 18. The composition according to claim 16, characterized in that the oligomeric phosphate ester of a compound of formula (V) or (VI), corresponds

wherein each R is independently hydrogen, C 1 -C 4 alkyl or hydroxy, n is 1 to 3, and o is 1 to 10. 19. The composition according to claim 16, characterized in that the compound of the formula (VII) corresponds

wherein R _{3 is} methyl or phenyl, x = 1 to 20, each R is independently hydrogen, C 1 -C ₄ alkyl or hydroxy, and n = 1 to 3. 20. The composition according to claim 16, characterized in that the cyclic phosphonate corresponds to a compound of formula (VIII),

wherein R 3 is methyl or phenyl, each R is independently hydrogen, C 1 -C ₄ alkyl or hydroxy and y is 0 or 2. 21. The composition according to claim 16, characterized in that the phosphinate ester is selected from benzene monophenyl ester derivative or a phosphaphenanthrene derivative of the formula (IX) or (X)

Composition according to Claim 9, characterized in that component (ii-b) is polyol, aminouracil, POSS compounds, Trishydroxyethylisocyanurat, melamine cyanurate and / or expandable graphite. 23. A composition according to claim 22, characterized in that the polyol is selected from pentaerythritol, dipentaerythritol, tripentaerythritol or Mixtures thereof and / or the aminouracil is 1, 3-dimethyl-6-aminouracil and / or the POSS compound is methylsiloxane-based. 24. The composition according to any one of claims 9 to 23, further comprising a polymer or a polymer mixture, characterized in that the Concentration of the sum of the components (i) and (ii-a) and / or (ii-b) in the polymer or the polymer mixture 0.1 to 60 wt .-%, based on the polymer or the polymer mixture. 25. A composition according to claim 24, characterized in that the polymer is a thermoplastic, preferably selected from the group consisting of polyamide, polycarbonate, polyolefin, polystyrene, polyester, polyvinyl chloride, Polyvinyl alcohol, polymethacrylate, polyacrylate, ABS and polyurethane, a biopolymer is based on polylactic acid and / or starch or a thermoset, preferably selected from the group consisting of epoxy resin, phenolic resin and Melamine resin, or a polymer blend comprising two or more of these polymers. 26. Use of a composition according to any one of claims 9 to 25 as a flame retardant in a polymer or a polymer blend, paper, textiles or wood plastic composites (WPC). 27. The composition according to any one of the preceding claims, wherein in the compound of formula (III) Y = S is. 28. A metal thiophosphonate of the formula (III), wherein Mt is selected from Cu, Ca, Mg, Zn, Mn, Fe, Al, Co, Ni, Sn, TiO, Zr, ZrO, Ce, MoO, WO 2, VO, B, Si, La, Ti, Bi or Sb; Y = S and n = 2 or 3.