# US 11,028,324 B2 · Flame retardant mixtures, the production and the use thereof

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- Number: US 11,028,324 B2
- Document ID: US11028324B2
- Status: Granted
- Kind: B2
- Application number: 16/318,526
- Filed: 2017-07-12
- Published: 2019-10-17
- Granted: 2021-06-08
- Earliest claimed: 2016-07-20
- Assignees: Clariant Plastics & Coatings Ltd
- Applicants: Clariant Plastics & Coatings Ltd
- Inventors: Harald Bauer; Sebastian Hörold; Martin Sicken
- Web page: https://patentgrep.com/patent/US11028324B2

## CPC

- C09K 21/12: containing phosphorus
- C08J 3/203: {Solid polymers with solid and/or liquid additives}
- C08K 3/32: Phosphorus-containing compounds
- C08K 5/0066: {Flame-proofing or flame-retarding additives}
- C08K 5/5377: Phosphinous compounds, e.g. R2=P—OR'
- C08K 5/5393: Phosphonous compounds, e.g. R—P(OR')2
- C09K 21/04: containing phosphorus
- C08K 3/016: Flame-proofing or flame-retarding additives
- C08K 3/38: Boron-containing compounds
- C08K 5/5205: {Salts of P-acids with N-bases}
- C08K 7/14: Glass
- C08K 2003/321: {Phosphates}
- C08K 2003/328: {Phosphates of heavy metals}
- C08K 2003/387: {Borates}
- C08K 2201/005: Additives being defined by their particle size in general
- C08K 2201/006: Additives being defined by their surface area
- C08K 2201/014: Additives containing two or more different additives of the same subgroup in C08K
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

The invention relates to a flame retardant mixture comprising 99.9999% to 87% by weight of diorganylphosphinic acid salts as component A) and 0.0001% to 13% by weight of iron as component B), where the sum total of A) and B) is 100% by weight. The invention likewise relates to processes for producing the aforementioned flame retardant mixture and to the use thereof.

## Claims

### Claim 1

A flame retardant mixture comprising:
99.9999% to 75% by weight of diorganylphosphinic acid salt as component A); and
0.0001% to 13% by weight of iron in the form of an iron-containing substance B1) as component B), where the amount of B1) is 0.0001% to 25% by weight,
where the sum total of A) and B1) is 100% by weight,
wherein the diorganylphosphinic acid salts conform to the formula (II)
wherein
R1 and R2 are the same or different and are independently methyl, ethyl, n-propyl, isopropyl, butyl, n-butyl, tert-butyl, n-pentyl, 2-pentyl, 3 pentyl, 2-methylbutyl, 3-methylbutyl (isopentyl), 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl (neopentyl), hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclopentylethyl, cyclohexyl, cyclohexylethyl, phenyl, phenylethyl, methylphenyl and/or methylphenylethyl,
m is 1 to 4, and
M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na and/or K,
and wherein component B1) is present in the form of (a) iron(II) bis and/or iron(III) tris: -(diethylphosphinate), -(dipropylphosphinate), -(butylethylphosphinate), -(n-butylethylphosphinate), -(sec-butylethylphosphinate), -(hexylethylphosphinate), -(dibutylphosphinate), -(hexylbutylphosphinate), -(octylethylphosphinate), -(ethyl(cyclopentylethyl)phosphinate), -(butyl(cyclopentylethyl)phosphinate), -(ethyl(cyclohexylethyl)phosphinate), -(butyl(cyclohexylethyl)phosphinate), -(ethyl(phenylethyl)phosphinate), -(butyl(phenylethyl)phosphinate), -(ethyl(4-methylphenylethyl)phosphinate), -(butyl(4-methylphenylethyl)phosphinate), -(butylcyclopentylphosphinate), -(butylcyclohexylethylphosphinate), -(butylphenylphosphinate), -(ethyl(4-methylphenyl)phosphinate) and/or -(butyl(4-methylphenyl)phosphinate); (b) iron(II) mono and/or iron(III) mono: -(ethylphosphinate), -(propylphosphinate), -(butylphosphinate), -(n-butylphosphinate), -(sec-butylphosphinate), -(hexylphosphinate) and/or -(octylphosphinate); (c) iron(II) and/or iron(III): ethylphosphonate, propylphosphonate, butylphosphonate, n-butylphosphonate, sec-butylphosphonate, hexylphosphonate, octylphosphonate, and/or (d) iron(II) and/or iron(III) salts of: ethyl(cyclopentylethyl)phosphinic acid, butyl(cyclopentylethyl)phosphinic acid, ethyl(cyclohexylethyl)phosphinic acid, butyl(cyclohexylethyl)phosphinic acid, ethyl(phenylethyl)phosphinic acid, butyl(phenylethyl)phosphinic acid, ethyl(4-methylphenylethyl)phosphinic acid, ethylphenylphosphinic acid, butyl(4-methylphenylethyl)phosphinic acid, butylcyclopentylphosphinic acid, butylcyclohexylethylphosphinic acid, butylphenylphosphinic acid, ethyl(4-methylphenyl)phosphinic acid, butyl(4-methylphenyl)phosphinic acid, ethylphosphinylacetic acid and/or ethylphosphinylbutyric acid, hydroxymethyl(ethyl)ethylphosphinic acid, 1 hydroxy-1-methylpropylethylphosphinic acid, butyl ethylphosphonate, acylethylphosphonic anhydride, butylethylphosphonic acid, butylethylphosphinic acid, ethylphosphinylisobutyronitrile (1-cyano-1-methylethylethylphosphinic acid), propylethylphosphinic acid, t-butyl ethylphosphonate, t-butylethylphosphinic acid, hydroxymethyl(butyl)ethylphosphinic acid, 3-hydroxy-3-methylpentylethylphosphinic acid, propoxyethylethylphosphinic acid, phenylethylethylphosphinic acid, 2-ethylphosphinylethyl laurate, ethylpentylphosphinic acid, t-butoxyethylethylphosphinic acid, ethylphosphinylisohexanonitrile, hexylethylphosphinic acid and/or ethylphosphinylethyl sulfate.

### Claim 2 (depends on 1)

The flame retardant mixture as claimed in claim 1, which comprises 99.9995% to 95% by weight of component A) and 0.0005% to 5% by weight of component B).

### Claim 3 (depends on 1)

The flame retardant mixture as claimed in claim 1, wherein components A) and B1) are in the form of a physical mixture.

### Claim 4 (depends on 1)

The flame retardant mixture as claimed in claim 1, which comprises:
99.8999% to 75% by weight of component A),
0.0001% to 20% by weight of component B1), and a further component C), wherein component C) is a compound,
where the sum total of components A), B1) and C) is 100% by weight, with the proviso that components A), B1) and C) are each different compounds.

### Claim 5 (depends on 4)

The flame retardant mixture as claimed in claim 4, wherein components A), B1) and C) are in the form of a physical mixture with one another.

### Claim 6 (depends on 4)

The flame retardant mixture as claimed in claim 4, wherein components A) and C) form a homogeneous chemical compound with one another and they are in the form of a physical mixture with component B1).

### Claim 7 (depends on 4)

The flame retardant mixture as claimed in claim 4, wherein component C) comprises telomers of the formula (III)
H—(CwH2w)kP(O)(OM)(CxH2x)l-H (III)
where, in formula (III), independently of one another,
k is 1 to 9,
l is 1 to 9,
w is 2 to 9,
x is 2 to 9, 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,
and the (CwH2w)k, (CxH2x)l groups may be linear or branched;
and/or the telomers are those of the formula (I)
where
R3, R4 are the same or different and are C6-C10-arylene, C7-C20-alkylarylene, C7-C20-arylalkylene and/or C3-C16-cycloalkyl or -bicycloalkyl,
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; and
components A), B1) and C) are different compounds.

### Claim 8 (depends on 7)

The flame retardant mixture as claimed in claim 7, wherein, in formula (III), w and x are each 2 or 3 and k and l are each 1 to 3 and M is Al, Ti, Fe or Zn.

### Claim 9 (depends on 7)

The flame retardant mixture as claimed in claim 7, wherein the telomers are metal salts of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid, ethyloctylphosphinic acid, sec-butylethylphosphinic acid, 1-ethylbutyl(butyl)phosphinic acid, ethyl(1-methylpentyl)phosphinic acid, di-sec-butylphosphinic to acid, di-1-methylpropylphosphinic acid, propyl(hexyl)phosphinic acid, dihexylphosphinic acid, hexyl(nonyl)phosphinic acid, propyl(nonyl)phosphinic acid, dinonylphosphinic acid, dipropylphosphinic acid, butyl(octyl)phosphinic acid, hexyl(octyl)phosphinic acid, dioctylphosphinic acid, ethyl(cyclopentylethyl)phosphinic acid, butyl(cyclopentylethyl)phosphinic acid, ethyl(cyclohexylethyl)phosphinic acid, butyl(cyclohexylethyl)phosphinic acid, ethyl(phenylethyl)phosphinic acid, butyl(phenylethyl)phosphinic acid, ethyl(4-methylphenylethyl)phosphinic acid, butyl(4-methylphenylethyl)phosphinic acid, butylcyclopentylphosphinic acid, butylcyclohexylethylphosphinic acid, butylphenylphosphinic acid, ethyl(4-methylphenyl)phosphinic acid and/or butyl(4-methylphenyl)phosphinic acid, ethylphosphinylisobutyronitrile (1-cyano-1-methylethylethylphosphinic acid), propylethylphosphinic acid, hydroxymethyl(butyl)ethylphosphinic acid, 3-hydroxy-3-methylpentylethylphosphinic acid, propoxyethylethylphosphinic acid, phenylethylethylphosphinic acid, ethylpentylphosphinic acid, t-butoxyethylethylphosphinic acid, ethylphosphinylisohexanonitrile, hexylethylphosphinic acid and/or ethylphosphinylethyl sulfate, where the metal of the metal salt comes from the group of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na and/or K.

### Claim 10 (depends on 4)

The flame retardant mixture as claimed in claim 4, which further comprises synergists as component D), where the synergists are melamine phosphate, dimelamine phosphate, pentamelamine triphosphate, trimelamine diphosphate, tetrakismelamine triphosphate, hexakismelamine pentaphosphate, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate, melamine polyphosphates, melam polyphosphates, melem polyphosphates and/or melon polyphosphates; or melamine condensation products, as melam, melem and/or melon; or oligomeric esters of tris(hydroxyethyl) isocyanurate with aromatic polycarboxylic acids, benzoguanamine, tris(hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine, melamine cyanurate, urea cyanurate, dicyandiamide and/or guanidine; or nitrogen-containing phosphates of the formula (NH4)yH3-yPO4 or (NH4PO3)z with y=1 to 3 and z=1 to 10 000; or aluminum phosphites, aluminum pyrophosphites, aluminum phosphonates, aluminum pyrophosphonates; or silicates, zeolites, silicas, ceramic powder, zinc compounds, tin oxide hydrate, magnesium hydroxide, hydrotalcite, magnesium carbonate and/or calcium magnesium carbonate.

### Claim 11 (depends on 10)

The flame retardant mixture as claimed in claim 10, which comprises:
a) component A),
b) component B1),
c) component C), and
d) component D),
where the sum total of A), B1), C) and D) is 100% by weight, with the proviso that A), B1) and C) are different compounds.

### Claim 12 (depends on 1)

The flame retardant mixture as claimed in claim 1, which comprises:
a particle size of 0.01 to 1000 μm,
a bulk density of 50 to 1500 g/L,
a tamped density of 100 g/L to 1100 g/L,
an angle of repose of 5 to 45 degrees,
a BET surface area of 1 to 40 m2/g,
L color values of 85 to 99.9,
a color values of -4 to +9, and
b color values of -2 to +6.

### Claim 13 (depends on 1)

The flame retardant mixture as claimed in claim 1, which comprises:
a particle size of 0.5 to 800 μm,
a bulk density of 80 to 800 g/L,
a tamped density of 600 g/L to 800 g/L, and
an angle of repose of 10 to 40 degrees.

### Claim 14 (depends on 0, 1)

A flame-retardant thermoplastic or thermoset polymer molding composition or polymer molding, film, filament or fiber comprising 0.5% to 50% by weight of flame retardant mixtures as claimed in claim 1, 0.5% to 95% by weight of thermoplastic or thermoset polymer or mixtures thereof, 0% to 55% by weight of additives and 0% to 70% by weight of filler or reinforcing materials, where the sum of the components is 100% by weight; and where the polymer comprises thermoplastic polymers of the HI (high-impact) polystyrene, polyphenylene ether, polyamide, polyester or polycarbonate, and blends or polymer blends of the ABS (acrylonitrile-butadiene-styrene) or PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) or PPE/HIPS (polyphenylene ether/HI polystyrene) polymer, and/or thermoset polymers of the formaldehyde-, epoxide- or melamine-phenolic resin polymer, unsaturated polyester, epoxy resin and/or polyurethane.

### Claim 15 (depends on 14)

The thermoplastic or thermoset polymer molding composition, polymer molding, film, filament or fiber as claimed in claim 14, which comprises antioxidants, UV stabilizers, gamma ray stabilizers, hydrolysis stabilizers, antistats, emulsifiers, nucleating agents, plasticizers, processing auxiliaries, impact modifiers, dyes, or pigments.