Azine metal phosphates as flame-retardant materials
The present invention relates to azine metal phosphates, compositions containing the same, a process for preparing the same and their use as flame retardants. Typical representatives are (A-H) (+) [MtPO 4 ] (+) .2H 2 O and (Mel-H) (+) [AlP 2 O 7 ] (+) (where A=melamine or guanidine, Mel=melamine and Mt=Mg or Zn).
1. An azine metal phosphate of the general formula [I],
[(A-H) (+) [N m+ (PO 4 ) x (3−) (P 2 O 7 ) y (4−) ] − .pH 2 O] z [I]
where (A-H) (+) is selected from (melamine-H) + of the formula (I-H), (melam-H) + of the formula (II-H), (guanamine-H) + of the formula (III-H), where R is methyl or phenyl, or [(amino)guanidine-H] + of the formula (IV-H), where R′ is hydrogen or amino,
M=Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, TiO, ZrO, VO, B, Si, Al, Sb, La, Ti, Zr, Ce, Bi, or Sn,
m=2 or 3,
x and y are each, independently of one another, 0 or 1,
p is an integer from 0 to 4 and
z is an integer >5,
where 1+m=3x+4y.
2. A composition comprising
(i) an azine metal phosphate as claimed in claim 1 ,
(ii) a metal-containing component different from the component (i), and
(iii) optionally a metal-free component.
3. The composition as claimed in claim 2 , characterized in that the metal-containing component (ii) is selected from metal hydroxide, metal phosphate, metal pyrophosphate, bismelamine zinc diphosphate, bismelamine magnesium diphosphate, bismelamine aluminum triphosphate, hydrotalcite, hydrocalumite, zeolite, cationically or anionically modified organoclay, stannate salt or molybdate salt, metal borate or metal phosphinate of the formula (V) or (VI), metal phosphonate of the formula (VII) or mixtures thereof,
where R 1 and R 2 are each, independently of one another, hydrogen, linear or branched C 1 -C 6 -alkyl or phenyl; Mt 1 =Ca, Mg, Zn, or Al, m=2 or 3, and Mt=Ca, Mg, Zn, Al, Sn, Zr, TiO, ZrO, Ce, MoO, WO 2 , VO, Mn, Bi, or Sb, D=O or S, and n is 2 or 3.
4. The composition as claimed in claim 2 , characterized in that the metal-free component (iii) is selected from red phosphorus, oligomeric phosphate ester, oligomeric phosphonate ester, cyclic phosphonate ester, thiopyrophosphoric ester, melamine orthophosphate, melam, melem, melamine phenyl phosphinate, monomeric, oligomeric or polymeric melamine phenyl phosphonate, ammonium polyphosphate, hydroxyalkylphosphine oxide, tetrakishydroxyalkylphosphonium salt, phospholane (oxide) derivative, dihydrophosphole (oxide) derivative, phosphinate ester, or mixtures thereof.
5. The composition as claimed in claim 4 , characterized in that the oligomeric phosphate ester corresponds to the formula (VIII) or (IX), and/or the oligomeric phosphonate ester corresponds to the formula (X),
where each R is independently hydrogen, C 1 -C 4 -alkyl, or hydroxy, R 3 is methyl or phenyl, x is an integer from 1 to 20, n=1, 2, or 3, and o is an integer from 1 to 10.
6. The composition as claimed in claim 4 , characterized in that the cyclic phosphonate ester corresponds to the formula (XI),
where R is hydrogen, C 1 -C 4 -alkyl, or hydroxy, R 3 is methyl or phenyl, and y=0 or 2.
7. The composition as claimed in claim 4 , characterized in that the thiopyrophosphoric ester corresponds to the formula (XII),
where each R 1 and R 2 is independently hydrogen, C 1 -C 4 -alkyl, or hydroxy.
8. The composition as claimed in claim 4 , characterized in that the phosphinate ester is selected from a benzenemonophenyl ester derivative, a 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide derivative or 6H-dibenzo(c,e)(1,2)oxaphosphorin-6-one derivative of the formula (XIII) or (XIV), 10-benzyl-9-oxa-10-phosphaphenanthrene 10-oxide, or mixtures thereof:
9. The composition as claimed in claim 2 further comprising a polymer or a polymer mixture, characterized in that the concentration of the sum of the components (i) and (ii) in the polymer or the polymer mixture is from 0.1 to 60% by weight, based on the polymer or the polymer mixture.
10. The composition as claimed in claim 9 , characterized in that the polymer is a thermoplastic, a biopolymer based on polylactic acid and/or starch, a thermoset, or mixtures thereof.
11. A process for preparing azine metal phosphates of the general formula [I],
[(A-H) (+) [N m+ (PO 4 ) x (3−) (P 2 O 7 ) y (4−) ] − .p H 2 O] z [I]
where (A-H) (+) is selected from (melamine-H) + of the formula (I-H), (melam-H) + of the formula (II-H), [(aceto)benzoguanamine-H] + of the formula (III-H), where R is methyl or phenyl, or [(amino)guanidine-H] + of the formula (IV-H), where R′ is hydrogen or amino,
M=Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, TiO, ZrO, VO, B, Si, Al, Sb, La, Ti, Zr, Ce, Bi or Sn,
m=2 or 3,
x and y are each, independently of one another, 0 or 1,
p is an integer from 0 to 4 and
z is an integer >5,
where 1+m=3x+4y,
by reacting an azine starting material (A) with a metal oxide starting material (B) and orthophosphoric acid (C),
wherein the azine starting material (A) is selected from melamine of the formula (I), melam of the formula (II), guanamine of the formula (III), or guanidine (bi)carbonate of the formula (IV), and the metal oxide starting material (B) is selected from metal oxides, metal hydroxides, metal carbonates, or a combination thereof,
12. The process as claimed in claim 11 , characterized in that the components (A) and (B) are initially charged as a mixture in water and orthophosphoric acid (C) is added.
13. The process as claimed in claim 11 , characterized in that the reaction is carried out at from 20 to 90° C.
14. The process as claimed in claim 11 , characterized in that the components (A):(B):(C) are present in a molar ratio of (1 to 3):(1):(1 to 3), with azine phosphates being additionally present outside the stoichiometry of 1:1:1.
15. The process as claimed in claim 11 , characterized in that the reaction product is tempered at from 220 to 350° C.
16. The composition as claimed in claim 3 , characterized in that the zeolite comprises zeolite X, zeolite Y, or a combination thereof.
17. The composition as claimed in claim 10 , characterized in that the thermoplastic is selected from the group consisting of polyamide, polycarbonate, polyolefin, polystyrene, polyester, polyvinyl chloride, polyvinyl alcohol, acrylonitrile butadiene styrene (ABS), and polyurethane.
18. The composition as claimed in claim 10 , characterized in that the thermoset is selected from the group consisting of epoxy resin, phenolic resin, melamine resin, and a combination thereof.
19. The process as claimed in claim 12 , wherein the mixture is a suspension.
20. The process as claimed in claim 13 , wherein the reaction is carried out at from 30 to 70° C.