# US 2015/0148464 A1 · Flame retardant compositions of phosphinic acid salts and nitroxyl derivatives

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- Number: US 2015/0148464 A1
- Document ID: US20150148464A1
- Status: Published application
- Kind: A1
- Application number: 14/614,001
- Filed: 2015-02-04
- Published: 2015-05-28
- Earliest claimed: 2010-03-25
- Assignees: BASF SE
- Applicants: BASF SE
- Inventors: Rainer XALTER
- Web page: https://patentgrep.com/patent/US20150148464A1

## CPC

- C08K 5/5313: Phosphinic compounds, e.g. R2=P(:O)OR'
- C08K 5/34926: {also containing heterocyclic groups other than triazine groups}
- C08K 5/5205: {Salts of P-acids with N-bases}
- C09K 21/12: containing phosphorus
- C08K 5/0066: {Flame-proofing or flame-retarding additives}
- C08K 5/3435: Piperidines
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE

## Abstract

The present invention relates to flame retardant polymer compositions which comprise mixtures of salts of phosphinic acids and 2,2,6,6-tetraalkylpiperidines. The mixtures are especially useful for the manufacture of flame retardant compositions based on thermoplastic polymers.

## Claims

### Claim 1

A composition, which comprises
a) A salt of a phosphinic acid as represented by the structural formulae
in which
one of R1 and R2 represents hydrogen or C1-C8alkyl; or both R1 and R2 represent C1-C8alkyl; and
R3 represents C1-C10alkylene, C2-C10alkylene interrupted by phenylene, phenylene, (C1-C4alkyl)1-3phenylene, or phenyl-C1-C4alkylene;
b) A tetraalkylpiperidine or tetraalkylpiperazine derivative selected from the group that consists of 2,2,6,6-tetraalkylpiperidine-1-oxides, 1-hydroxy-2,2,6,6-tetraalkylpiperidines, 1-alkoxy-2,2,6,6-tetraalkylpiperidines, 1-acyloxy-2,2,6,6-piperidines, 1-hydroxy-2,2,6,6-tetraalkylpiperazines, 1-alkoxy-2,2,6,6-tetraalkylpiperazines, and 1-acyloxy-2,2,6,6-piperazines; and
c) A polymer substrate.

### Claim 2 (depends on 1)

A composition according to claim 1, wherein the salt of a phosphinic acid (I) of Component a) is represented by the formula
in which
one of R1 and R2 represents hydrogen or C1-C8alkyl; or both R1 and R2 represent C1-C8alkyl;
M represents (C1-C4alkyl)4N, (C1-C4alkyl)3NH, (C2-C4alkylOH)4N, (C2-C4alkylOH)3NH, (C2-C4alkylOH)2N(CH3)2, (C2-C4alkylOH)2NHCH3, (C6H5)4N, (C6H5)3NH, (C6H5CH3)4N, (C6H5CH3)3NH, NH4, melamine, guanidine, an alkali metal or earth alkali metal ion, or an aluminium, zinc, iron or boron ion;
m is a numeral from 1-3 and indicates the number of positive charges on M; and
n is a numeral from 1-3 and indicates the number of phosphinic acid anions corresponding to Mm+.

### Claim 3 (depends on 2)

A composition according to claim 2, wherein the salt of a phosphinic acid (I) of Component a) is represented by the formula

### Claim 4 (depends on 1)

A composition according to claim 1, which comprises
a) The aluminium salt of a phosphinic acid (I), as represented by the formula
b) A tetraalkylpiperidine derivative selected from the group that consists of 2,2,6,6-tetraalkylpiperidine-1-oxides, 1-hydroxy-2,2,6,6-tetraalkylpiperidines, 1-alkoxy-2,2,6,6-tetraalkylpiperidines and 1-acyloxy-2,2,6,6-piperidines; and
c) A thermoplastic polymer substrate.

### Claim 5 (depends on 1)

A composition according to claim 1, which comprises as Component b) at least one tetraalkylpiperidine derivative selected from the group that consists of 2,2,6,6-tetraalkylpiperidine-1-oxides of the formula
1-hydroxy-2,2,6,6-tetraalkylpiperidines of the formula
1-alkoxy-2,2,6,6-tetraalkylpiperidines of the formula
and
1-acyloxy-2,2,6,6-piperidines of the formula
Wherein
One of Ra and Rb represents
Hydrogen or an N-substituent and the other one represents an O-substituent or a C-substituent; or
Both Ra and Rb represent hydrogen, O-substituents or C-substituents;
R represents C1-C20alkyl, C5-C6cycloalkyl or C2-C20alkyl, C5-C6cycloalkyl or C2-C20alkenyl with additional substituents;
Ac represents the acyl group of a C1-C20carboxylic acid; and
R1-R4 each represent C1-C4alkyl; and
R5 and R6, independently of one another, represent hydrogen or a substituent selected from the group consisting of C1-C4-alkyl, C1-C3alkylphenyl and phenyl; and
R5 and R6 together represent oxo.

### Claim 6 (depends on 5)

A composition according to claim 5, which comprises as Component b) at least one tetraalkylpiperidine derivative III a, III b, III c or III d,
Wherein
One of Ra and Rb represents
Hydrogen or an N-substituent and the other one represents an O-substituent or a C-substituent; or
Both Ra and Rb represent hydrogen, O-substituents or C-substituents;
R represents C1-C8alkyl, C5-C6cycloalkyl or C2-C8alkyl, C5-C6cycloalkyl or C2-C8alkenyl with additional substituents;
Ac represents the acyl group of a C1-C8carboxylic acid; and
R1-R4 are each methyl; and
R5 and R6 each represent hydrogen.

### Claim 7 (depends on 5)

A composition according to claim 5, which comprises as Component b) at least one tetraalkylpiperidine derivative III a, III b, III c or III d,
Wherein
One of Ra and Rb represents
Hydrogen or an N-substituent and the other one represents an O-substituent or a C-substituent; or
Both Ra and Rb represent O-substituents or C-substituents;
R represents C1-C8alkyl, C5-C6cycloalkyl or C2-C8alkyl, C5-C6cycloalkyl or C2-C8alkenyl substituted by hydroxy;
Ac represents the acyl group of a C1-C8carboxylic acid; and
R1-R4 are each methyl; and
R5 and R6 each represent hydrogen.

### Claim 8 (depends on 5)

A composition according to claim 5, which comprises as Component b) at least one tetraalkylpiperidine derivative III c or III d selected from the group consisting of
1-Cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine,
bis(1-Octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
2,4-bis[(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-(2-hydroxyethylamino-s-triazine,
bis(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,
2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazine,
1-(2-Hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine,
1-(2-Hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine,
1-(2-Hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,
bis(1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
bis(1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) adipate,
2,4-bis{N-[1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethylamino)-s-triazine,
The reaction product of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-butylamino]-6-chloro-s-triazine with N,N′-bis(3-aminopropyl)ethylenediamine), 2,4-bis[(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-(2-hydroxyethylamino-s-triazine,
The oligomeric compound which is the condensation product of 4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine,
The compound of the formula
And the compound of the formula
in which n is from 1 to 15.

### Claim 9 (depends on 1)

A composition according to claim 1, which comprises
a) A salt of a phosphinic acid as represented by the structural formulae (I) or (II), in which
one of R1 and R2 represents hydrogen or C1-C8alkyl; or both R1 and R2 represent C1-C8alkyl; and
R3 represents C1-C10alkylene, C2-C10alkylene interrupted by phenylene, phenylene, (C1-C4alkyl)1-3phenylene, or phenyl-C1-C4alkylene;
b) At least one tetraalkylpiperidine derivative III c or III d selected from the group consisting of
1-Cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine, bis(1-Octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
2,4-bis[(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-(2-hydroxyethylamino-s-triazine,
bis(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate, 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazine,
1-(2-Hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine,
1-(2-Hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine,
1-(2-Hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,
bis(1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
bis(1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) adipate,
2,4-bis{N-[1-(2-Hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethylamino)-s-triazine,
The reaction product of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazine with N,N′-bis(3-aminopropyl)ethylenediamine), 2,4-bis[(1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-(2-hydroxyethylamino-s-triazine,
The oligomeric compound which is the condensation product of 4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine,
The compound of the formula
And the compound of the formula
in which n is from 1 to 15; and
c) A thermoplastic polymer selected from the group consisting of polyolefin homopolymers and copolymers of olefins with each other or with vinyl monomers.

### Claim 10 (depends on 1)

A composition according to claim 1 for use as a flame retardant.

### Claim 11

A mixture, which comprises
a) A salt of a phosphinic acid as represented by the structural formulae
in which
one of R1 and R2 represents hydrogen or C1-C8alkyl; or both R1 and R2 represent C1-C8alkyl; and
R3 represents C1-C10alkylene, C2-C10alkylene interrupted by phenylene, phenylene, (C1-C4alkyl)1-3phenylene, or phenyl-C1-C4alkylene;
b) A tetraalkylpiperidine derivative selected from the group that consists of 2,2,6,6-tetraalkylpiperidine-1-oxides, 1-hydroxy-2,2,6,6-tetraalkylpiperidines, 1-alkoxy-2,2,6,6-tetraalkylpiperidines and 1-acyloxy-2,2,6,6-piperidines.

### Claim 12 (depends on 1)

A process for imparting flame retardancy to a polymer substrate, which process comprises adding to a polymer substrate of Component c) the mixture according to claim 1.