Flame retardant mixtures and production thereof

Abstract

Flame retardant mixtures comprising as component (A) 30% to 99.9% by weight of dialkylphosphinic salts of the formula (II), a and b may be the same or different and are each independently 1 to 9, and where the carbon chains may be linear, branched or cyclic 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 m is 1 to 4, as component (B) 0.1% to 70% by weight of alkyl hydroxyalkylphosphinyl organylcarboxylic acid salts and/or ester salts of the formula (I) where R1CyH2y+1 with y=2 to 8, R2, R3, R4, R5, R6 are the same or different and are each independently H, CxH2x+1, CxH2x1, CxH2x3, CxH2xCO2X, CxH2x2CO2X, CxH2x4CO2X, (C2H3CO2X)u and u=0 to 1000000, CO2X, CxH2x(P(O)(OM)R1), CxH2x2(P(O)(OM)R1)(CO2X) and/or CH2CO2X, where, in the R1, R2, R3, R4, R5 and R6 groups, the carbon chains may be linear, branched or cyclic, M is Mg, Ca, Al, Sb, Sn, Ge, Fe, Ti, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, H and/or N-containing cations, x is 1 to 25, X is H, M, CzH2z+1 and z is 1 to 8, with the proviso that at least one of the R2, R3, R4, R5, R6 groups is not H, and the compounds of formula (II) and formula (I) are different compounds.

Claims

1. A flame retardant mixture comprising: as component (A) 30 to 99.9 wt % of dialkylphosphinic salts of the formula (II) ##STR00003## wherein: a and b are identical or different and, independently of one another, are each 1 to 9, wherein the carbon chains are linear, branched or cyclic, and M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, a protonated nitrogen base or a combination thereof, and m is 1 to 4, as component (B) 0.1 to 70 wt % of a compound of the formula (I) ##STR00004## wherein: R.sup.1 is C.sub.yH.sub.2yi with y=2 to 8, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are identical or different and, independently of one another, are H, C.sub.xH.sub.2x+1, C.sub.xH.sub.2x1, C.sub.xH.sub.2x3, C.sub.xH.sub.2xCO.sub.2X, C.sub.xH.sub.2x2CO.sub.2X, C.sub.xH.sub.2x4CO.sub.2X, CO.sub.2X, C.sub.xH.sub.2x(P(O)(OM)R.sup.1), C.sub.xH.sub.2x2(P(O)(OM)R.sup.1)(CO.sub.2X), CH.sub.2CO.sub.2X or a combination thereof, R.sup.6 is C.sub.xH.sub.2xCO.sub.2X, C.sub.xH.sub.2x2CO.sub.2X, C.sub.xH.sub.2x4CO.sub.2X, CO.sub.2X, C.sub.xH.sub.2x(P(O)(OM)R.sup.1), C.sub.xH.sub.2x2(P(O)(OM)R.sup.1)(CO.sub.2X) or CH.sub.2CO.sub.2X, wherein the carbon chains in the groups R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6 are linear, branched, or cyclic, M is Mg, Ca, Al, Sb, Sn, Ge, Fe, Ti, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, H, a N-containing cation or a combination thereof, m is 1 to 4, x is 1 to 25, X is H, M or C.sub.2H.sub.2z+1, and z is 1 to 8, where the compounds of the formula (II) and the formula (I) are different compounds.

2. The flame retardant mixture as claimed in claim 1, comprising: as component (A) 50 to 99.9 wt % of dialkylphosphinic salts of the formula(II), and as component (B) 0.1 to 50 wt % of a compound of the formula (I).

3. The flame retardant mixture as claimed in claim 1, comprising: as component (A) 90 to 99.8 wt % of dialkylphosphinic salts of the formula(II), and as component (B) 0.2 to 10 wt % of a compound of the formula (I).

4. The flame retardant mixture as claimed in claim 1, wherein a and b in formula (II) are identical or different and, independently of one another, are each 1, 2 or 3.

5. The flame retardant mixture as claimed in claim 1, wherein a and b in formula (II) are identical and are each 1.

6. The flame retardant mixture as claimed in claim 1, further comprising telomers.

7. The flame retardant mixture as claimed in claim 6, comprising: as component (A) 30 to 99.8 wt % of dialkylphosphinic salts of the formula(II), as component (B) 0.1 to 50 wt % of a compound of the formula (I), and as component (C) 0.1 to 20 wt % of telomers of the formula (III)
C.sub.vH.sub.2v+1(C.sub.wH.sub.2w).sub.kP(O)(OM)(C.sub.xH.sub.2x).sub.lC.sub.zH.sub.2z+1 wherein, independently of one another, v is 2 to 9, w is 2 to 9, x is 2 to 9, z is 2 to 9, k is 0 to 9, l is 0 to 9, and M is H, Mg, Ca, Al, Sb, Sn, Ge, Ti, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K or a combination thereof, and the groups C.sub.vH.sub.2v+1, (C.sub.wH.sub.2w).sub.k, (C.sub.xH.sub.2x)l, and C.sub.zH.sub.2z+1 are linear, branched or cyclic, and wherein the compounds of the formulae (I), (II), and (III) are each different.

8. The flame retardant mixture as claimed in claim 7, comprising: as component (A) 74.5 to 97 wt % of dialkylphosphinic salts of the formula(II), as component (B) 2.5 to 25.5 wt % of a compound of the formula (I), and as component (C) 0.5 to 4.8 wt % of telomers of the formula (III).

9. The flame retardant mixture as claimed in claim 6, wherein the telomers comprise ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid, ethyloctylphosphinic acid, sec-butyl(ethyl)phosphinic acid, 1-ethylbutyl(butyl)phosphinic acid, ethyl(1-methylpentyl)phosphinic acid, di-sec-butylphosphinic acid (di-1-methylpropylphosphinic acid), propyl(hexyl)phosphinic acid, dihexylphosphinic acid, hexyl(nonyl)phosphinic acid, dinonylphosphinic acid, salts thereof or a combination thereof.

10. The flame retardant mixture as claimed in claim 6, wherein the telomers are ethylbutylphosphinic acid, ethyl-n-butylphosphinic acid, ethyl-sec-butylphosphinic acid, propyl(hexyl)phosphinic acid, dihexylphosphinic acid, salts thereof or a combination thereof.

11. The flame retardant mixture as claimed in claim 1, wherein M in formula (I) is Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Mn or a combination thereof.

12. The flame retardant mixture as claimed in claim 1, wherein component (B) comprises Al, Zn, Fe and/or Ti salts of carboxyoctadecyl(ethyl)phosphinic acid, of methylcarboxyoctadecyl(ethyl)phosphinic acid, of carboxyethyl(ethyl)phosphinic acid, of 1,2-dicarboxyethyl(ethyl)phosphinic acid, of 2,3-dicarboxypropyl(ethyl)phosphinic acid, or a combination thereof.

13. The flame retardant mixture as claimed in claim 1, wherein component (B) comprises Al and/or Zn salts of carboxyoctadecyl(ethyl)phosphinic acid, of methylcarboxyoctadecyl(ethyl)phosphinic acid, of carboxyethyl(ethyl)phosphinic acid, of 1,2-dicarboxyethyl(ethyl)phosphinic acid, of 2,3-dicarboxypropylphosphinic acid, or a combination thereof.

14. The flame retardant mixture as claimed in claim 1, further comprising additives selected from the group consisting of antioxidants, antistats, blowing agents, other flame retardants, heat stabilizers, impact modifiers, process auxiliaries, lubricants, light stabilizers, antidripping agents, compatibilizers, reinforcing agents, fillers, seed-forming agents, nucleating agents, laser marking additives, hydrolysis stabilizers, chain extenders, color pigments, plasticizers, plastifying agents and combinations thereof.

15. The flame retardant mixture as claimed in claim 1, having a mean particle size d.sub.50 of 0.02-900 m, a bulk density of 100 to 680 g/L, and a color value (Hunter L value) of 93 to 97.

16. The flame retardant mixture as claimed in claim 1, having a mean particle size d.sub.50 of 0.1-110 m and a bulk density of 250 to 620 g/L.

17. A process for producing a flame retardant mixture as claimed in claim 1, comprising the steps of: a) reacting a water-soluble salt of hypophosphorous acid or hypophosphorous acid in a ratio of 100 mol:0.1 mol to 50 mol:50 mol with an alkenecarboxylic acid, b) reacting the product from step a) with an olefin in the ratio of 100 mol of phosphinic acid source: 1800 to 50 mol of olefin, c) reacting the product from step b) with a metal salt to give a flame retardant mixture composed of dialkylphosphinic salts of the formula (II) with a compound of the formula (I).

18. A process for producing a flame retardant mixture as claimed in claim 1, comprising the steps of: a) reacting a salt of hypophosphorous acid having a solubility in water of less than 10 g/100 g, or hypophosphorous acid, in a ratio of 100 mol:0.1 mol to 50 mol:50 mol with an alkenecarboxylic acid and b) reacting the product from step a) with an olefin in the ratio of 100 mol of water-soluble salt of hypophosphorous acid or hypophosphorous acid: 1800 to 50 mol.

19. A process for producing a flame retardant mixture as claimed in claim 1, comprising the steps of: a) reacting a water-soluble salt of hypophosphorous acid or hypophosphorous acid in a ratio of 100 mol:0.1 mol to 50 mol:50 mol with an alkenecarboxylic acid, b) reacting the product from step a) with an olefin in the ratio of 100 mol of water-soluble salt of hypophosphorous acid or hypophosphorous acid: 99.9 to 50 mol of olefin, c) reacting the product from step b) with a metal salt to give the flame retardant mixture, and d) physically admixing telomers.

20. A flame retardant, a flame retardant for clear varnishes and intumescent coatings, as a flame retardant for wood and other cellulosic products, a reactive and/or nonreactive flame retardant for polymers, a flame-retardant polymer molding composition, a flame-retardant polymer molding, a flame-retardant polyester fabric, a flame-retardant pure and blended cellulose fabric, an intermediate, a binder, a crosslinker and/or accelerator in the curing of epoxy resins, polyurethanes, and unsaturated polyester resins, a polymer stabilizer, a crop protectant, a sequestrant, a mineral oil additive, a corrosion inhibitor, a laundry detergent, a cleaning product or electronic product comprising a flame retardant mixture as claimed in claim 1.

21. A plug connector, a current-bearing component in power distributors (residual current protection), a circuit board, a power plug, a circuit breaker, a lamp housing, an LED lamp housing, a capacitor housing, a coil element, a ventilator, a grounding contact, a plug, a housing for plugs, a cable, a flexible printed circuit board, a charging cable, a motor cover, or a textile coating comprising a flame retardant mixture as claimed in claim 1.

22. A flame-retardant thermoplastic or thermoset polymer molding composition comprising: 0.5 to 45 wt % of one or more flame retardant mixture as claimed in claim 1, 10 to 95 wt % of a thermoplastic polymer, a thermoset polymer or a mixture thereof, 0 to 55 wt % of additives, and 0 to 55 wt % of filler, reinforcing materials or a combination thereof, the sum of the components being 100 wt %.

23. A flame-retardant thermoplastic or thermoset polymer molding, film, filament or fiber comprising: 5 to 30 wt % of one or more flame retardant mixtures as claimed in claim 1, 20 to 95 wt % of a thermoplastic polymer, thermoset polymer or a mixture thereof, 5 to 55 wt % of additives, and 10 to 55 wt % of filler, reinforcing materials or a combination thereof, the sum of the components being 100 wt %.

Description

EXAMPLE 1

(1) In process stage 1, in accordance with table 1, 140 g (1.59 mol) of sodium hypophosphite (NHP) were introduced with 423 g of demineralized water in an N.sub.2-purged five-neck flask (dropping funnel, stirrer, reflux condenser, thermometer) and heated to 80 C. Over the course of 6 h, a solution of 11.4 g (0.16 mol) of acrylic acid and 0.57 g of Na.sub.2S.sub.2O.sub.8 in 112 g of water was added dropwise.

(2) In process stage 2, the resulting solution, in accordance with table 2, was diluted with 139 g of H.sub.2O and introduced into a Bchi glass autoclave suitable for pressurized gas work. At 120 C. and 4 bar ethylene pressure, approximately 5.3 g of initiator (in solution in 72 g of water) were metered in over the course of 3 h. 81 g of ethylene are taken up.

(3) In process stage 3, in a five-neck, round-bottom flask with stirrer, thermometer, reflux condenser, and two dropping funnels, in accordance with table 3, 564 g of demineralized water are introduced at 85 C. and the solution from process stage 2 is metered in simultaneously with the corresponding amount of aluminum sulfate (table 3) over 2 h.

(4) While still hot, the solution is filtered off on a suction filter and washed with hot demineralized water. After 15-hour drying at 120 C. in a drying oven rendered inert with nitrogen, the product is isolated.

(5) Table 3 gives the yield, residual moisture content (RM), phosphorus content and aluminum content, the amount of alkyl-hydroxyphosphinyl-alkanecarboxylic salt and of telomer, and table 4 gives the DMT value.

(6) As is apparent from the tables, the flame retardant mixture of the invention with alkyl-hydroxyphosphinyl-alkanoic salt based on acrylic acid exhibits much less interaction with the polymer than commercially available aluminum diethylphosphinate. In the .sup.31P NMR spectrum, the alkyl-hydroxyphosphinyl-alkanecarboxylic salt shows a chemical shift of 47.5 ppm (multiplet).

EXAMPLE 2

(7) In the same way as for example 1, acrylic acid and sodium hypophosphite are reacted, but over the course of only 2 h. Furthermore, in analogy to example 1, reaction takes place with ethylene and with aluminum sulfate. The reactant quantities and reaction parameters are set out in tables 1, 2, and 3.

(8) In the .sup.31P NMR spectrum, the resultant alkyl-hydroxyphosphinyl-alkanecarboxylic salt has a chemical shift of 47.5 ppm.

(9) Table 3 gives the yield, residual moisture content (RM), phosphorus content and aluminum content, and the amount of alkyl-hydroxyphosphinyl-alkanoic salt and of telomer.

EXAMPLE 3

(10) As in example 1, acrylic acid and sodium hypophosphite are reacted in process stage 1, but for a period of 12 h. Furthermore, in analogy to example 1, reaction takes place with ethylene and with aluminum sulfate. The reactant quantities and reaction parameters are set out in tables 1, 2, and 3.

(11) In the .sup.31P NMR spectrum, the resultant alkyl-hydroxyphosphinyl-alkanoic salt has a chemical shift of 47.5 ppm.

(12) In spite of the longer reaction time in process stage 1, the amount of acrylic acid adduct is no higher than in example 1: there is no after-reaction.

(13) Table 3 gives the yield, residual moisture content (RM), phosphorus content and aluminum content, and the amount of alkyl-hydroxyphosphinyl-alkanoic salt and of telomer.

EXAMPLE 4

(14) In process stage 1, in accordance with table 1, 140 g of sodium hypophosphite (1.59 mol) were introduced with 384 g of glacial acetic acid and 44.9 g of oleic acid in an N.sub.2-purged five-neck flask (dropping funnel, stirrer, reflux condenser, thermometer) and heated to 80 C. Over the course of 4 h a solution of 44.9 g (0.16 mol) of oleic acid and 5.68 g of Na.sub.2S.sub.2O.sub.8 in 112 g of water was added dropwise.

(15) The resulting solution is first evaporated to dryness under reduced pressure and thereafter made up to the original mass using demineralized water. An additional 106 g of H.sub.2O were added and the whole was introduced into a Bchi glass autoclave suitable for pressurized gas work. In process stage 2, at 120 C. and 4 bar ethylene pressure, approximately 5.3 g of initiator (in solution in 72 g of water) are metered in over the course of 3 h. 82 g of ethylene are taken up. The resulting solution was introduced with 327 g of Al sulfate solution simultaneously over 2 h into a five-neck, round-bottom flask with stirrer, thermometer, reflux condenser, and two dropping funnels, which had been charged at 85 C. with 564 g of demineralized water. The solution thus obtained, while still hot, is filtered off on a suction filter and washed with hot demineralized water. After 15-hour drying at 120 C. in a drying oven rendered inert using nitrogen, product (alkyl-hydroxyphosphinyl-alkanoic salt) is isolated.

(16) In the .sup.31P NMR spectrum, it exhibits a chemical shift of 49.3 ppm (doublet). Table 3 gives the yield, residual moisture content (RM), phosphorus content and aluminum content, and the amount of alkyl-hydroxyphosphinyl-alkanoic salt and of telomer, and table 4 gives the DMT value.

(17) As is apparent from the tables, the flame retardant mixture of the invention with alkyl-hydroxyphosphinyl-alkanecarboxylic salt based on acrylic acid exhibits much less interaction with the polymer than commercially available aluminum diethylphosphinate.

EXAMPLE 5

(18) In analogy to the procedure in example 4, linoleic acid and sodium hypophosphite are reacted, but at 100 C., 8 h, and with bisbenzoyl peroxide initiator. Furthermore, in the other process stages, in analogy to example 1, reaction takes place with ethylene and with aluminum sulfate.

(19) In the .sup.31P NMR spectrum, the resultant alkyl-hydroxyphosphinyl-alkanecarboxylic salt has a number of signals in the region of a chemical shift of 49.5-50.8 ppm. The reactant quantities and reaction parameters are set out in tables 1, 2, and 3. Table 3 gives the yield, residual moisture content (RM), phosphorus content and aluminum content, and the amount of alkyl-hydroxyphosphinyl-alkanecarboxylic salt and of telomer.

EXAMPLE 6

(20) In analogy to example 1, maleic anhydride (which hydrolyzes to maleic acid in the aqueous solution) and sodium hypophosphite are reacted, but at 100 C. Furthermore, in analogy to example 1, reaction takes place with ethylene and with aluminum sulfate.

(21) In the .sup.31P NMR spectrum, the resultant alkyl-hydroxyphosphinyl-alkanecarboxylic salt has a chemical shift of 42.9 ppm (singlet).

(22) The reactant quantities and reaction parameters are set out in tables 1, 2, and 3. Table 3 gives the yield, residual moisture content (RM), phosphorus content and aluminum content, and the amount of alkyl-hydroxyphosphinyl-alkanoic salt and of telomer.

EXAMPLE 7

(23) In analogy to example 1, fumaric acid and sodium hypophosphite are reacted, but at 100 C. Furthermore, in analogy to example 1, reaction takes place with ethylene and with aluminum sulfate.

(24) The reactant quantities and reaction parameters are set out in tables 1, 2, and 3. Table 3 gives the yield, residual moisture content (RM), phosphorus content and aluminum content, and the amount of alkyl-hydroxyphosphinyl-alkanecarboxylic salt and of telomer.

EXAMPLE 8

(25) In analogy to example 4, methyl oleate and sodium hypophosphite are reacted, but at 118 C. Furthermore, in analogy to example 1, reaction takes place with ethylene and with aluminum sulfate.

(26) The reactant quantities and reaction parameters are set out in tables 1, 2, and 3. In the .sup.31P NMR spectrum, the resultant alkyl-hydroxyphosphinyl-alkanecarboxylic ester salt has a number of signals in the region of a chemical shift of around 49 ppm (multiplet).

(27) Table 3 gives the yield, residual moisture content (RM), phosphorus content and aluminum content, and the amount of alkyl-hydroxyphosphinyl-alkanecarboxylic ester salt and of telomer for the resultant product, and also the DMT value in table 4.

(28) The flame retardant mixture of the invention with alkyl-hydroxyphosphinyl-alkanecarboxylic ester salt therefore exhibits much less interaction with the polymer than commercially available aluminum diethylphosphinate.

EXAMPLE 9

(29) As in example 4, in process stage 1, oleic acid and sodium hypophosphite are reacted, but for 6 h. Furthermore, in process stage 2, in analogy to example 1, reaction takes place with ethylene, and in process stage 3 with aluminum sulfate. The quantities and parameters are set out in tables 1-3.

(30) A five-neck, round-bottom flask with stirrer, thermometer, reflux condenser, and two dropping funnels is charged with 435 g of demineralized water at 80 C. The solution from process stage 2 and 456 g of zinc sulfate solution (11.4% Zn) are metered in simultaneously over 2 h. While still hot, the resulting solution is filtered off on a suction filter and washed with hot demineralized water. After 15-hour drying at 120 C. in a drying oven rendered inert with nitrogen, the product is isolated.

(31) In the .sup.31P NMR spectrum, the resulting alkyl-hydroxyphosphinyl-alkanecarboxylic salt has a number of signals in the region of a chemical shift of about 49 ppm (multiplet).

(32) Table 3 gives the yield, residual moisture content (RM), phosphorus content and aluminum content, and the amount of alkyl-hydroxyphosphinyl-alkanecarboxylic salt and of telomer for the resultant product, and also the DMT value in table 4. The flame retardant mixture of the invention with alkyl-hydroxyphosphinyl-alkanecarboxylic salt exhibits much less interaction with the polymer than commercial aluminum diethylphosphinate.

EXAMPLE 10

(33) As in example 1, acrylic acid and sodium hypophosphite are reacted. Subsequently, however, reaction takes place with propylene and with aluminum sulfate.

(34) The reactant quantities and reaction parameters are set out in tables 1, 2 and 3. In the .sup.31P NMR spectrum, the resulting alkyl-hydroxyphosphinyl-alkanecarboxylic salt has a number of signals in the region of a chemical shift of about 46.5 ppm (multiplet).

(35) Table 3 gives the yield, residual moisture content (RM), phosphorus content and aluminum content, and the amount of alkyl-hydroxyphosphinyl-alkanecarboxylic salt and of telomer for the resultant product, and also the DMT value in table 4. The flame retardant mixture of the invention with alkyl-hydroxyphosphinyl-alkanecarboxylic salt based on acrylic acid exhibits much less interaction with the polymer than commercially available aluminum diethylphosphinate.

(36) TABLE-US-00008 TABLE 1 Alkene- Process stage 1 carboxylic Glacial H.sub.2O for acid NHP acetic ACA Initiator initiator Time Temperature Example (ACA) [mol] [g] H.sub.2O acid [g] type [g] [g] [h] [ C.] 1 Acrylic acid 1.59 140 423 11.4 Na.sub.2S.sub.2O.sub.8 0.57 112 6 80 2 Acrylic acid 1.59 140 423 11.4 Na.sub.2S.sub.2O.sub.8 0.57 112 2 80 3 Acrylic acid 1.59 140 423 11.4 Na.sub.2S.sub.2O.sub.8 0.57 112 12 80 4 Oleic acid 1.59 140 384 44.91 Na.sub.2S.sub.2O.sub.8 5.68 112 4 80 5 Linoleic acid 1.59 140 423 8.982 bisbenzoyl 5.78 8 100 peroxide 6 Maleic acid 1.59 140 423 15.6 Na.sub.2S.sub.2O.sub.8 0.38 38 6 100 7 Fumaric acid 1.59 140 423 18.4 Na.sub.2S.sub.2O.sub.8 0.38 38 6 100 8 Methyl oleate 1.59 140 423 47.14 Na.sub.2S.sub.2O.sub.8 3.03 112 8 118 9 Oleic acid 1.59 140 423 44.91 Na.sub.2S.sub.2O.sub.8 5.68 112 6 80 10 Acrylic acid 1.59 140 423 11.4 Na.sub.2S.sub.2O.sub.8 0.57 56 6 80

(37) TABLE-US-00009 TABLE 2 Process stage 2 Process H.sub.2O for H.sub.2O Olefin Initiator initiator Time Temperature Example [g] Olefin [g] type [g] [g] [h] [ C.] 1 139 Ethylene 81 Na.sub.2S.sub.2O.sub.8 5.3 72 2.83 120 2 139 Ethylene 81 Na.sub.2S.sub.2O.sub.8 5.3 72 3.00 120 3 139 Ethylene 81 Na.sub.2S.sub.2O.sub.8 5.3 72 3.00 120 4 106 Ethylene 82 Na.sub.2S.sub.2O.sub.8 5.3 72 3.00 120 5 217.8 Ethylene 80 Na.sub.2S.sub.2O.sub.8 5.3 72 3.00 120 6 253 Ethylene 78 Na.sub.2S.sub.2O.sub.8 4.1 55 2.58 120 7 253 Ethylene 77 Na.sub.2S.sub.2O.sub.8 4.1 55 2.58 120 8 103.3 Ethylene 80 Na.sub.2S.sub.2O.sub.8 5.3 72 3.00 120 9 105.5 Ethylene 82 Na.sub.2S.sub.2O.sub.8 5.3 72 3.00 120 10 139 Propylene 127 Na.sub.2S.sub.2O.sub.8 10.6 72 4.25 120

(38) TABLE-US-00010 TABLE 3 Process stage 3 H.sub.2O Metal salt Time Temperature Yield RM P Al (or Zn) P/Al AHPOS Telomer Example [g] type [mol] [g] [h] [ C.] [%] [wt %] [wt %] [wt %] [mol/mol] [wt %] [wt %] 1 564 Al sulfate 0.53 327 2 85 95.1 0.29 23.2 6.7 3.02 7.2 1.1 2 564 Al sulfate 0.53 327 2 85 94.8 0.19 23.1 6.7 3.00 2.5 1.1 3 564 Al sulfate 0.53 327 2 85 94.1 0.35 23.2 6.8 2.97 7.1 1.1 4 564 Al sulfate 0.53 327 2 85 82.2 0.25 20.7 6.2 2.90 19.9 0.5 5 564 Al sulfate 0.53 327 2 85 83.1 0.25 18.8 5.5 2.98 7.4 2.9 6 580 Al sulfate 0.53 327 2 85 86.8 0.35 23.0 6.8 2.95 4.9 1.1 7 580 Al sulfate 0.53 327 2 85 85.7 0.21 22.9 6.6 3.02 6.5 4.8 8 564 Al sulfate 0.53 327 2 85 83.4 0.20 19.7 5.7 3.01 25.5 1.1 9 435 Zn sulfate 0.795 456 2 80 82.6 0.41 17.7 18.8 1.98 18.9 2.2 10 564 Al sulfate 0.53 327 2 85 94.1 0.15 19.1 5.5 3.02 7.6 1.9 Alkyl-hydroxyphosphinyl-organylic acid (AHPOS) - .sup.31P NMR, chemical shift: aluminum diethylphosphinate 50.24 ppm Al sulfate: 4.37% AlZn sulfate: 11.4% Zn

(39) TABLE-US-00011 TABLE 4 DMT Example [mg MeOH/kg product] 1 54 4 42 8 38 9 42 10 56 Commercial aluminum diethylphosphinate 1 150 (containing 0.5 wt % of telomers) Commercial aluminum diethylphosphinate 2 160 (containing 4.8 wt % of telomers)

(40) The commercial aluminum diethylphosphinate is free from alkyl-hydroxyphosphinyl-alkanecarboxylic salts. Its DMT value is much higher than that of products of the invention, which therefore exhibit substantially better properties, including in respect of subsequent processing in a polymer.

EXAMPLE 11

(41) Using the product from example 1 (based on acrylic acid), in accordance with the general protocol Production, Processing and Testing of flame-retardant polymer molding compositions and polymer moldings, a flame-retardant PBT molding is produced, having the best flame retardancy classification V-0 and having better notched impact toughness than commercial aluminum diethylphosphinate (comparison with example 14 from table 5).

EXAMPLE 12

(42) Using the product from example 4 (based on oleic acid), in accordance with the general protocol Production, Processing and Testing of flame-retardant polymer molding compositions and polymer moldings, a flame-retardant PBT molding is produced, having the best flame retardancy classification V-0 and having better notched impact toughness than commercial aluminum diethylphosphinate (comparison with example 14 from table 5).

EXAMPLE 13

(43) Using the product from example 8 (based on methyl oleate), in accordance with the general protocol Production, Processing and Testing of flame-retardant polymer molding compositions and polymer moldings, a flame-retardant PBT molding is produced, having the best flame retardancy classification V-0 and having better notched impact toughness than commercial aluminum diethylphosphinate (comparison with example 14 from table 5).

EXAMPLE 14 (COMPARATIVE)

(44) Using commercial aluminum diethylphosphinate, in accordance with the general protocol Production, Processing and Testing of flame-retardant polymer molding compositions and polymer moldings, a flame-retardant PBT molding is produced, having the best flame retardancy classification V-0 but with a poorer notched impact toughness than with the flame retardant mixtures of the invention (table 5).

EXAMPLE 15 (COMPARATIVE)

(45) Using no flame retardant, a PBT molding is produced according to the general protocol Production, Processing and Testing of flame-retardant polymer molding compositions and polymer moldings. The moldings do not meet the stated object of flame retardancy, are consumed completely in burning, and do not achieve any flame retardancy classification. The greater notched impact toughness is attributable solely to the lower solids content and higher polymer content (table 5).

(46) TABLE-US-00012 TABLE 5 Example 14 14a 15 11 12 13 (comp.) (comp.) comp.) Product from example 1 [wt %] 20.0 Product from example 4 [wt %] 20.0 Product from example 8 [wt %] 20.0 Commercial aluminum [wt %] 20.0 diethylphosphinate 1 Commercial aluminum [wt %] 20 diethylphosphinate 2 PBT [wt %] 49.7 49.7 49.7 49.7 49.7 69.7 GF [wt %] 30.0 30.0 30.0 30.0 30.0 30.0 Wax [wt %] 0.3 0.3 0.3 0.3 0.3 0.3 UL 94 (1.6 mm) [Classification] V-0 V-0 V-0 V-0 V-0 unclass Notched impact toughness [J/cm.sup.2] 6.9 6.7 6.2 5.7 5.5 7.9 PBT = Ultradur B 4500 natural GF = PPG glass fiber HP 3786 EC 104.5 MM Commercial aluminum diethylphosphinate: Exolit OP 1230 Wax = Licowax E gran., PDEF2 050112 [Classification] = classification; unclass = burnt up without flame retardancy effect