Nanoparticulate phosphorus-containing flame retardant system
The invention relates to a nanoparticulate phosphorus-containing flame retardant system, which comprises a phosphinic salt of the formula (I) and/or a diphosphinic salt of the formula (II) and/or 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, Zn, 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 to a process for the preparation of these flame retardant systems, and to their use.
1 . A nanoparticulate phosphorus-containing flame retardant system, 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,
wherein
R 1 and R 2 are identical or different and are C 1 -C 6 -alkyl, linear or branched, and/or 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, Zn, 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.
2 . The nanoparticulate phosphorus-containing flame retardant system 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.
3 . The nanoparticulate phosphorus-containing flame retardant system 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.
4 . The nanoparticulate phosphorus-containing flame retardant system 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-butyinaphthylene, phenylmethylene, phenylethylene, phenylpropylene, or phenylbutylene.
5 . The nanoparticulate phosphorus-containing flame retardant system as claimed in claim 1 , having a particle size sfrom 1 to 1000 nm.
6 . The nanoparticulate phosphorus-containing flame retardant system as claimed in claim 1 , wherein the BET surface area is from 2 to 1000 m 2 /g.
7 . The nanoparticulate phosphorus-containing flame retardant system as claimed in claim 1 , further comprising from 0.01 to 10% by weight of at least one of a protective colloids or a crystallization modifier.
8 . A process for the preparation of a nanoparticulate phosphorus-containing flame retardant system as claimed in claim 1 , comprising the step of reacting
A) an aluminum/zinc/titanium/zirconium compound, a tin compound or a mixture thereof with
B) a soluble compound of phosphinic acid of the formula (I) a diphosphinic acid of the formula (II) a polymer of the phosphinic acid. a polymer of the diphosphinic acid or a mixture thereof, and, optionally,
C) from 0.01 to 10% by weight of at least one of a protective colloid and a crystallization modifier,
to form the flame retardant system and optionally, isolating the flame retardant system, drying the flame retardant system, and grinding the flame retardant system.
9 . A process for the preparation of a nanoparticulate phosphorus-containing flame retardant system as claimed in claim 1 , comprising the steps of
A) hydrolyzing an aluminum/titanium/zinc/tin compound, a zirconium compound, and
B) reacting the product with a soluble compound of phosphinic acid of the formula (I) the diphosphinic acid of the formula (II) a polymer of the phosphinic acid. a polymer of the diphosphinic acid or a mixture thereof, or performing the hydrolyzing step in the presence of a soluble compound of phosihinic acid of the formula (I) the diphosphinic acid of the formula (II) a polymer of the phosphinic acid, a Polymer of the diphosphinic acid or a mixture thereof to form the flame retardant system, and, optionally, isolating the flame retardant system, drying the flame retardant system, and grinding the flame retardant system.
10 . The process as claimed in claim 8 , wherein the reaction is conducted in at least one of a microreactor or minireactor.
11 . The process as claimed in claim 8 , wherein the metal charge equivalentimol of phosphorus ratio A:B in which components A) and B) are used is from 100:1 to 1:100.
12 . The process as claimed in claim 8 , wherein the temperature is from 0 to 300° C., the reaction time is from 1*10 −7 to 1*10 2 h, and the pressure is from 1 to 200 MPa.
13 . The process as claimed in claim 10 , wherein the throughput in the microreactor is from 10 −3 l/h to 10 3 l/h, and in the minireactor is from 10 2 l/h to 10 5 l/h.
14 . A process for the preparation of a nanoparticulate phosphorus-containing flame retardant system as claimed in claim 1 , comprising the steps of wet-grinding a non-nanoparticulate phosphorus-containing flame retardant system to a particle size to from 1 to 1000 nm, and, optionally, adding from 0.01 to 10% by weight of at least one of a protective colloid or crystallization modifier to form a nanoparticulate phosphorus-containing flame retardant system, and optionally, isolating the nanoparticulate phosphorus-containing flame retardant system drying the nanoparticulate phosphorus-containing flame retardant system, and grinding the nanoparticulate phosphorus-containing flame retardant system.
15 . The process as claimed in claim 14 , wherein the non-nanoparticulate phosphorus-containing flame retardant system is dispersed at a concentration of from 0.1 to 50% by weight in a solvent, wherein the temperature is from 0 to 300° C., the reaction time is from 1*10 −7 to 1*10 2 h, and the pressure is from 1 to 200 MPa.
16 . The process as claimed in claim 8 , wherein the reacting step takes place in the presence of a solvent and the isolation of the nanoparticulate phosphorus-containing flame retardant system from the solvent takes place via filtration, sedimentation, or centrifuging.
17 . The process as claimed in claim 8 , wherein the reacting step produces ancillary components and wherein the isolation of the nanoparticulate phosphorus-containing flame retardant system from the ancillary components takes place via treatment with a solvent in a ratio of from 1:100 to 100:1 parts by weight, and isolation of the nanoparticulate phosphorus-containing flame retardant system from the solvent via filtration, sedimentation, or centrifuging.
18 . The process as claimed in claim 8 , wherein the drying step takes place in one or more stages at a pressure of from 10 Pa to 100 MPa, for a period of from 0.01 to 1000 h, and at a temperature of from −20 to +500° C.
19 . The process as claimed in claim 8 , wherein the grinding step occurs in at least one of a hammer mill, impact mill, vibratory mill, roll mill, floating-roller mill or air-jet mill.
20 . The process as claimed in claim 8 , wherein component B is dispersed in a solvent and the concentration of component B in the solvent is from 0.1 to 50% by weight of phosphorus.
21 . The process as claimed in one or more of claims 8 to 20 , wherein the aluminum/titanium/zinc/tin compound, zirconium compound or mixture thereof is an organic compound.
22 . A polymer article comprising a nanoparticulate phosphorus-containing flame retardant system as claimed in claim 1 , wherein the polymer article is a polymer molding composition, polymer molding, polymer filament, polymer film or polymer fiber.
23 . A flame retardant composition comprising a nanoparticulate phosphorus-containing flame retardant system as claimed in claim 1 , wherein the flame retardant composition is a flame-retardant coating, gel coat, intumescent lacquer, clear lacquer, topcoat, adhesive or adhesion coating.
24 . The nanoparticulate phosphorus-containing flame retardant system as claimed in claim 1 , having a particle size from 5 to 500 nm.
25 . The nanoparticulate phosphorus-containing flame retardant system as claimed in claim 1 , wherein the BET surface area is from 5 to 500 m 2 /g.
26 . The process as claimed in claim 8 , wherein the metal charge equivalent/mol of phosphorus ratio A:B in which components A) and B) are used is from 10:1 to 1:10.
27 . The process as claimed in claim 14 , wherein the particle size is from 1 to 1000 nm.
28 . The process as claimed in claim 15 , wherein the non-nanoparticulate phosphorus-containing flame retardant system is dispersed at a concentration of from 1 to 20% by weight.
29 . The process as claimed in claim 18 , wherein the temperature is from 50 to 350° C.
30 . The process as claimed in claim 20 , wherein the concentration of component B in the solvent is from 1 to 30% by weight of phosphorus.
31 . A porous article impregnated with a nanoparticulate phosphorus-containing flame retardant system as claimed in claim 1 , wherein the porous article is wood, particle board, cork, paper or textile.