Compression-granulated flame retardant composition
The present invention relates to a compression-granulated flame retardant composition which comprises a phosphinic salt of the formula (I) and/or comprises a diphosphinic salt of the formula (II), and/or comprises their polymers, where R 1 and R 2 are identical or different and are C 1 -C 6 -alkyl, linear or branched, and/or aryl; R 3 is C 1 -C 10 -alkylene, linear or branched, C 6 -C 10 -arylene, -alkylarylene, or -arylalkylene; M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, and/or a protonated nitrogen base; m is from 1 to 4; n is from 1 to 4; x is from 1 to 4, and comprises a fusible zinc phosphinate; and to a process for preparation of this compression-granulated flame retardant composition, and to the use of the composition.
1 . A compression-granulated flame retardant composition, comprising a phosphinic salt of the formula (I), a diphosphinic salt of the formula (II), a polymer of the phosphinic salt, a polymer of the diphosphinic salt or a mixture thereof,
where
R 1 and R 2 are identical or different and are C 1 -C 6 -alkyl, linear or branched, or aryl; R 3 is C 1 -C 10 -alkylene, linear or branched, C 6 -C 10 -arylene, -alkylarylene, or -arylalkylene; M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, or a protonated nitrogen base; m is from 1 to 4; n is from 1 to 4; x is from 1 to 4, and
at least one fusible zinc compound selected from the group consisting of a fusible zinc phosphinate, a polymer of a fusible zinc phosphinate and a mixture thereof.
2 . The compression-granulated flame retardant composition as claimed in claim 1 , wherein M is calcium, aluminum, or titanium.
3 . The compression-granulated flame retardant composition as claimed in claim 1 , wherein R 1 and R 2 are identical or different and are C 1 -C 6 -alkyl, linear or branched, or phenyl.
4 . The compression-granulated flame retardant composition as claimed in claim 1 , wherein R 1 and R 2 are identical or different and are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, or phenyl.
5 . The compression-granulated flame retardant composition as claimed in claim 1 , wherein R 3 is methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene; phenylene, naphthylene; methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene, tert-butylnaphthylene; phenylmethylene, phenylethylene, phenylpropylene, or phenyl-butylene.
6 . The compression-granulated flame retardant composition as claimed in claim 1 , wherein the fusible zinc phosphinate and the polymer of the fusible zinc phosphinate are of the formula (I)
where R 1 and R 2 are identical or different and are hydrogen, C 1 -C 18 -alkyl, linear or branched, or aryl, and have a melting point of from 40 to 250° C.
7 . The compression-granulated flame retardant composition as claimed in claim 6 , wherein R 1 and R 2 are identical or different and are C 1 -C 6 -alkyl, linear or branched, or phenyl.
8 . The compression-granulated flame retardant composition as claimed in claim 6 , wherein R 1 and R 2 are identical or different and are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, or phenyl.
9 . The compression-granulated flame retardant composition as claimed in claim 1 , wherein the at least one fusible zinc compound is zinc dimethylphosphinate, zinc methylethylphosphinate, zinc diphenylphosphinate, or zinc diethylphosphinate.
10 . The compression-granulated flame retardant composition as claimed in claim 1 , wherein the at least one fusible zinc compound has a phosphorus content of from 10 to 35% by weight.
11 . The compression-granulated flame retardant composition as claimed in claim 1 , further comprising at least one synergist.
12 . The compression-granulated flame retardant composition as claimed in claim 11 , wherein the at least one synergist is melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphates, melam polyphosphates, melem polyphosphates, melon polyphosphates; melamine condensates, oligomeric esters of tris(hydroxyethyl) isocyanurate with aromatic polycarboxylic acids, benzoguanamine, tris(hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine, melamine cyanurate, dicyandiamide, or guanidine.
13 . The compression-granulated flame retardant composition as claimed in claim 11 , wherein the at least one synergist is a nitrogen-containing phosphate of the formulae (NH 4 ) y H 3-y PO 4 or (NH 4 PO 3 ) z , where y is from 1 to 3 and z is from 1 to 10 000.
14 . The compression-granulated flame retardant composition as claimed in claim 11 , wherein the at least one synergist is a nitrogen compound of the formulae (III) to (VIII), or a mixture thereof
where
R 5 to R 7 are hydrogen, C 1 -C 8 -alkyl, C 5 -C 16 -cycloalkyl or -alkylcycloalkyl, unsubstituted or substituted with a hydroxy function or with a C 1 -C 4 -hydroxyalkyl function, C 2 -C 8 -alkenyl, C 1 -C 8 -alkoxy, -acyl, -acyloxy, C 6 -C 12 -aryl or -arylalkyl, —OR 8 and —N(R 8 )R 9 , including systems of alicyclic-N or aromatic-N type,
R 8 is hydrogen, C 1 -C 8 -alkyl, C 5 -C 16 -cycloalkyl or -alkylcycloalkyl, unsubstituted or substituted with a hydroxy function or with a C 1 -C 4 -hydroxyalkyl function, C 2 -C 8 -alkenyl, C 1 -C 8 -alkoxy, -acyl, -acyloxy, or C 6 -C 12 -aryl or -arylalkyl,
R 9 to R 13 are the groups of R 8 , or —O—R 8 ,
m and n, independently of one another, are 1, 2, 3 or 4, and X is an acid which forms adducts with triazine compounds (III).
15 . The compression-granulated flame retardant composition as claimed in claim 11 , wherein the at least one synergist is zinc oxide, zinc hydroxide, zinc oxide hydrate, anhydrous zinc carbonate, basic zinc carbonate, zinc hydroxide carbonate, basic zinc carbonate hydrate, (basic) zinc silicate, zinc hexafluorosilicate, zinc stannate, zinc magnesium aluminum hydroxide carbonate, zinc hexafluorosilicate hexahydrate, zinc salts of the oxo acids of the third main group, zinc salts of the oxo acids of the fifth main group, zinc pyrophosphate, zinc salts of the oxo acids of the transition metals, zinc chromite, zinc molybdate, zinc permanganate, zinc molybdate magnesium silicate, or zinc permanganate.
16 . The compression-granulated flame retardant composition as claimed in claim 11 , wherein the at least one synergist has an organic anion.
17 . The compression-granulated flame retardant composition as claimed in claim 1 , further comprising at least one compound selected from the group consisting of carbodiimides, N,N′-dicyclohexylcarbodiimide, polyisocyanates, carbonylbiscaprolactam, styrene-acrylic polymers, sterically hindered phenols, sterically hindered amines, light stabilizers, phosphonites, antioxidants, and release agents.
18 . The compression-granulated flame retardant composition as claimed in claim 1 , having an average particle size from 100 to 2000 μm.
19 . The compression-granulated flame retardant composition as claimed in claim 1 , having an average bulk density from 200 to 1500 g/l.
20 . The compression-granulated flame retardant composition as claimed in claim 1 , having a dust content from 0.1 to 10% by weight, wherein the dust content is the fraction of flame retardant composition having a particle size below 20 μm.
21 . The compression-granulated flame retardant composition as claimed in claim 1 , having a phosphorus content from 8 to 50% by weight.
22 . The compression-granulated flame retardant composition as claimed in claim 1 comprising
a) from 50 to 98% by weight of the phosphinic salt of the formula (I), the diphosphinic salt of the formula (II), the polymer of the phosphinic salt, the polymer of the diphosphinic salt or a mixture thereof, and
b) from 2 to 50% by weight of the at least one fusible zinc compound.
23 . The compression-granulated flame retardant composition as claimed in claim 1 , comprising:
a) from 95 to 60% by weight of the phosphinic salt of the formula (I), the diphosphinic salt of the formula (II), the polymer of the phosphinic salt, the polymer of the diphosphinic salt or a mixture thereof, and
b) from 5 to 40% by weight of the at least one fusible zinc compound.
24 . The compression-granulated flame retardant composition as claimed in claim 1 , comprising:
a) from 8 to 90% by weight of the phosphinic salt of the formula (I), the diphosphinic salt of the formula (II), the polymer of the phosphinic salt, the polymer of the diphosphinic salt or a mixture thereof, and
b) from 2 to 50% by weight of the at least one fusible zinc compound, and
c) from 8 to 90% by weight of at least one synergist.
25 . The compression-granulated flame retardant composition as claimed in claim 1 , comprising:
a) from 10 to 85% by weight of the phosphinic salt of the formula (I), the diphosphinic salt of the formula (II), the polymer of the phosphinic salt, the polymer of the diphosphinic salt or a mixture thereof, and
b) from 5 to 40% by weight of the at least one fusible zinc compound, and
c) from 10 to 85% by weight of at least one synergist.
26 . A process for preparation of a compression-granulated flame retardant composition as claimed in claim 1 , comprising the steps of mixing the phosphinic salt of the formula (I), the diphosphinic salt of the formula (II), the polymer of the phosphinic salt, the polymer of the diphosphinic salt or a mixture thereof with the at least one fusible zinc compound at from 50 to 300° C. for from 0.01 to 1 hour to form a mixture, and compacting the mixture to give the compression-granulated material.
27 . A flame-retardant polymer molding composition comprising
from 1 to 50% by weight of a compression-granulated flame retardant composition as claimed in claim 1 , and
from 1 to 99% by weight of polymer or a mixture of polymers.
28 . A flame-retardant polymer molding composition comprising
from 1 to 50% by weight of a compression-granulated flame retardant composition as claimed in claim 1 ,
from 1 to 99% by weight of polymer or a mixture of polymers,
from 0.1 to 60% by weight of at least one additive, and
from 0.1 to 60% by weight of at least one of a filler or reinforcing material.
29 . A flame-retardant polymer molding composition comprising
from 5 to 30% by weight of a compression-granulated flame retardant composition as claimed in claim 1 ,
from 5 to 90% by weight of polymer of a mixture of polymers,
from 5 to 40% by weight of at least one additive,
from 5 to 40% by weight of at least one of a filler or reinforcing material.
30 . The molding composition as claimed in claim 27 , wherein the polymer or mixture of polymers is selected from the group consisting of thermoplastic polymers and thermoset polymers.
31 . A flame-retardant polymer article comprising
from 1 to 70% by weight of a compression-granulated flame retardant composition as claimed in claim 1 , and
from 1 to 99% by weight of polymer or a mixture of polymers,
wherein the polymer article is a polymer molding, polymer film, polymer filament, or polymer fiber.
32 . A flame-retardant polymer article comprising
from 1 to 70% by weight of a compression-granulated flame retardant composition as claimed in claim 1 ,
from 1 to 99% by weight of a polymer or a mixture of polymers,
from 0.1 to 60% by weight of at least one additive, and
from 0.1 to 60% by weight of at least one of a filler or reinforcing material, wherein,
the polymer article is in the form of a polymer molding, polymer film, polymer filament or polymer fiber.
33 . A flame-retardant polymer article comprising the flame-retardant polymer molding composition as claimed in claim 27 , wherein the polymer article is a polymer molding, polymer film, polymer filament, or polymer fiber.
34 . The polymer article as claimed in claim 33 , comprising
from 50 to 99% by weight of flame-retardant polymer molding composition.
35 . The polymer article as claimed in claim 33 , comprising
from 70 to 95% by weight of flame-retardant polymer molding composition.
36 . The flame-retardant polymer article as claimed in claim 33 , wherein the polymer or mixture of polymers are derived from polybutylene terephthalates, and the modulus of elasticity of the flame-retardant polymer molding, the flame-retardant polymer film, the flame-retardant polymer filament or the flame-retardant polymer fiber is from 10 000 to 12 000 MPa.
37 . The flame retardant polymer article as claimed in claim 33 , wherein the polymer or mixture of polymers are derived from nylon-6,6 polymers, and the modulus of elasticity of the flame-retardant polymer molding, the flame-retardant polymer film, the flame-retardant polymer filament or the flame-retardant polymer fiber is from 10 000 to 12 000 MPa.
38 . The flame-retardant polymer article as claimed in claim 33 , wherein the polymer or mixture of polymers are derived from nylon-6 polymers, and the modulus of elasticity of the flame-retardant polymer molding, the flame-retardant polymer film, the flame-retardant polymer filament or the flame-retardant polymer fiber is from 10 000 to 12 000 MPa.
39 . The compression-granulated flame retardant composition as claimed in claim 1 , wherein the at least one fusible zinc compound has a phosphorus content of from 15 to 25% by weight.
40 . The compression-granulated flame retardant composition as claimed in claim 16 , wherein the at least one synergist is a zinc salt of mono-, di-, oligo-, or polycarboxylic acid.
41 . The compression-granulated flame retardant composition as claimed in claim 40 , wherein the zinc salt of mono-, di-, oligo-, or polycarboxylic acid is a salt of formic acid, a salt of acetic acid, a salt of trifluoroacetic acid, zinc propionate, zinc butyrate, zinc valerate, zinc caprylate, zinc oleate, zinc stearate, a salt of oxalic acid, a salt of tartaric acid, a salt of citric acid, a salt of benzoic acid, zinc salicylate, a salt of lactic acid, a salt of acrylic acid, a salt of maleic acid, a salt of succinic acid, a salt of amino acids, a salt of acidic hydroxy functions, zinc para-phenolsulfonate, zinc para-phenolsulfonate hydrate, zinc acetylacetonate hydrate, zinc tannate, zinc dimethyldithiocarbamate, or zinc trifluoromethanesulfonate.
42 . The compression-granulated flame retardant composition as claimed in claim 1 , having an average particle size from 200 to 1000 μm.
43 . The compression-granulated flame retardant composition as claimed in claim 1 , having an average bulk density from 300 to 1000 g/l.
44 . The compression-granulated flame retardant composition as claimed in claim 1 , having a dust content from 0.5 to 5% by weight, wherein the dust content is the fraction of flame retardant composition having a particle size below 20 μm.
45 . The compression-granulated flame retardant composition as claimed in claim 1 , having a phosphorus content from 15.5 to 40% by weight.
46 . The compression-granulated flame retardant composition as claimed in claim 1 , having a phosphorus content from 16 to 25% by weight.
47 . The process as claimed in claim 26 , wherein the mixing step includes mixing at least one synergist with the phosphinic salt of the formula (I), the diphosphinic salt of the formula (II), the polymer of the phosphinic salt, the polymer of the diphosphinic salt or a mixture thereof and the at least one fusible zinc compound