POLYMERIC FLAME RETARDANT MIXTURES

Abstract

The invention relates to polymeric flame retardant mixtures containing a) 0.1 to 70 wt % dialkyl phosphinic acid salt, b) 0 to 20 wt % telomers, and c) 30 to 99.9 wt % oligomers, a), b) and c) adding up to 100 wt %, with the proviso that a), b) and c) are different compounds. The invention also relates to methods for synthesizing said polymeric flame retardant mixtures and the use thereof.

Claims

1. A polymeric flame retardant mixture comprising a) 0.1% to 70% by weight of dialkylphosphinic salt, b) 0% to 20% by weight of telomers, and c) 30% to 99.9% by weight of oligomers, where the sum total of a), b) and c) is 100% by weight, with the proviso that a) and b) are different compounds.

2. The polymeric flame retardant mixture as claimed in claim 1, comprising a) 2% to 50% by weight of dialkylphosphinic salt, b) 0.1% to 10% by weight of telomers, and c) 50% to 97.9% by weight of oligomers, where the sum total of a), b) and c) is 100% by weight, with the proviso that a) and b) are different compounds.

3. The polymeric flame retardant mixture as claimed in claim 1, wherein the dialkylphosphinic salts are those of the formula (V) ##STR00003## wherein a and b are the same or different and are each independently 1 to 9, and 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.

4. The polymeric flame retardant mixture as claimed in claim 1, wherein a and b in formula (V) are the same or different and are each independently 1, 2 or 3.

5. The polymeric flame retardant mixture as claimed in claim 1, wherein a and b in formula (V) are the same and are each 1.

6. The polymeric flame retardant mixture as claimed in claim 3, wherein M in formula (V) is Al, Ti, Fe or Zn.

7. The polymeric flame retardant mixture as claimed in claim 1, wherein the telomers are those of the formula (VI)
H(C.sub.wH.sub.2w).sub.kP(O)(OM)(C.sub.xH.sub.2x).sub.lH(VI) wherein, in formula (VI), 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, a protonated nitrogen base or a combination thereof, and the C.sub.wH.sub.2w).sub.k, (C.sub.xH.sub.2x).sub.l groups are linear or branched; and/or the telomers are those of the formula (I) ##STR00004## wherein R.sup.1, R.sup.2 are the same or different and are C.sub.6-C.sub.10-arylene, C.sub.7-C.sub.20-alkylarylene, C.sub.7-C.sub.20-arylalkylene and/or C.sub.3-C.sub.16-cycloalkyl or -bicycloalkyl, 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.

8. The polymeric flame retardant mixture as claimed in claim 7, wherein, in formula (VI), w and x are each 2 to 4 and k and l are each 1 to 4.

9. The polymeric flame retardant mixture as claimed in claim 7, wherein, in formula (VI), w and x are each 2 or 3 and k and l are each 1 to 3.

10. The polymeric flame retardant mixture as claimed in claim 7, wherein M in formula (VI), (I) or both is independently Al, Ti, Fe or Zn.

11. The polymeric flame retardant mixture as claimed in claim 1, 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 acid (di(1-methylpropyl)phosphinic 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, butyl(4-methylphenyl)phosphinic acid or a combination thereof, wherein the metal in the metal salt is selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and a combination thereof.

12. The polymeric flame retardant mixture as claimed in claim 1, wherein the oligomers are those of the formula (II)
R.sup.3[-E-(CR.sup.1R.sup.2).sub.k(CH.sub.2).sub.lCO].sub.nOR.sup.4(II) wherein n is 1-1 000 000, k is 0 to 5, l is 2 to 15, E is O or NH, R.sup.1 is H, R.sup.2 is CH.sub.3, R.sup.3 is H, CH.sub.3, COCH(CH.sub.3)OH or COC.sub.1-10-alkyl, R.sup.4 is H, CH(CH.sub.3)CO.sub.2H, COC.sub.1-10-alkyl or
(CH.sub.2).sub.mO[CO(CH.sub.2)l-(CR.sup.1R.sup.2).sub.k)-E].sub.nR.sup.3 wherein m is 1-20, R.sup.1 is H, R.sup.2 is CH.sub.3 and R.sup.3 is H, CH.sub.3 or C.sub.1-10-alkyl.

13. The polymeric flame retardant mixture as claimed in claim 1, wherein the oligomers are those of the formula (III)
[N(COR.sup.1)(CH.sub.2).sub.l].sub.n(Ill) wherein n is 1-1 000 000, l is 2 to 15 and R.sup.1 is CH.sub.3.

14. The polymeric flame retardant mixture as claimed in claim 1, wherein the oligomers are those of the formula (IV)
[O(CH.sub.2).sub.lCO].sub.n(IV) wherein n is 1-1 000 000, and l is 2 to 15.

15. The polymeric flame retardant mixture as claimed in claim 1, wherein the oligomers have a molar mass of 1000 g/mol to 114*10.sup.6 g/mol and a chain length n of 30 to 1 000 000.

16. The polymeric flame retardant mixture as claimed in claim 1, wherein the oligomers form from lactones, lactams or a combination thereof.

17. The polymeric flame retardant mixture as claimed in claim 16, wherein the lactones are propiolactone, gamma-butyrolactone, beta-butyrolactone, delta-valerolactone, epsilon-caprolactone or a combination thereof.

18. The polymeric flame retardant mixture as claimed in claim 16, wherein the lactams are propiolactam, gamma-butyrolactam, delta-valerolactam, epsilon-caprolactam, laurolactam, methylpyrrolidin-2-one or a combination thereof.

19. The polymeric flame retardant mixture as claimed in claim 1, further comprising synergists, 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, melon polyphosphates, melamine condensation products, oligomeric esters of tris(hydroxyethyl) isocyanurate with aromatic polycarboxylic acids, benzoguanamine, tris(hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine, melamine cyanurate, urea cyanurate, dicyandiamide, guanidine, nitrogen-containing phosphates of the formula (NH.sub.4).sub.yH.sub.3-yPO.sub.4 or (NH.sub.4PO.sub.3).sub.z with y=1 to 3 and z=1 to 10 000, aluminum phosphites, silicates, zeolites, silicas, ceramic powder, zinc compounds, tin oxide hydrate, magnesium hydroxide, hydrotalcite, magnesium carbonate, calcium magnesium carbonate or a combination thereof.

20. The polymeric flame retardant mixture as claimed in claim 19, comprising a) 0.1% to 70% by weight of dialkylphosphinic salt, b) 0% to 20% by weight of telomers, c) 30% to 99.8% by weight of oligomers, and d) 0.1% to 30% by weight of synergists, where the sum total of a), b), c) and d) is 100% by weight, with the proviso that a) and b) are different compounds.

21. A process for producing a polymeric flame retardant mixture as claimed in claim 1, comprising the step of incorporating nanoparticulate dialkylphosphinic salt containing 0% to 20% by weight of telomers into an oligomer without the use of catalysts.

22. The process as claimed in claim 21, wherein the incorporation is effected by extruding or kneading.

23. A process for producing a polymeric flame retardant mixture as claimed in claim 1, comprising the step of wet grinding standard particulate dialkylphosphinic salt having a particle size of 0.5 to 1000 m and containing 0% to 20% by weight of telomers in a short-chain oligomer until the particle size of 10 to 1000 m is attained.

24. The process as claimed in claim 23, wherein attainment of the desired particle size of 10 to 1000 m is followed by adjustment to a chain length n of 30 to 1 000 000 in a kneader.

25. The process as claimed in claim 23, wherein the reaction mixture is heated during the grinding to 20 to 160 C. for 0.1 to 72 h.

26. A fiber molding compound, film molding compound, fiber or film comprising a polymeric flame retardant mixture as claimed in claim 1.

27. A flame-retardant fiber molding compound, film molding compound, fiber or film comprising 0.1% to 80% by weight of a polymeric flame retardant mixture as claimed in claim 1 and 20% to 99.9% by weight of a thermoplastic or thermoset polymer.

28. A flame-retardant fiber molding compound, film molding compound, fiber or film comprising 0.1% to 50% by weight of a polymeric flame retardant mixture as claimed in claim 1, 50% to 99.9% by weight of a thermoplastic or thermoset polymer, 0% to 60% by weight of additives and 0% to 60% by weight of filler.

29. A flame retardant for clearcoats, intumescent coatings, wood, cellulose products, reactive flame retardants for polymers, non-reactive flame retardants for polymers, gelcoats, unsaturated polyester resins, production of flame-retardant polymer molding compounds, production of flame-retardant polymer moldings, rendering polyester and pure and blended cellulose fabrics flame-retardant by impregnation, polyurethane foams, polyolefins, unsaturated polyesters, phenolic resins or rendering textiles flame-retardant comprising a polymeric flame retardant mixture as claimed in claim 1.

30. (canceled)

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

Description

EXAMPLE 1

[0268] DPS-1 (150 g) is stirred into 200 g of epsilon-caprolactone with a spatula at room temperature. Then the grinding beads are added and grinding is effected with a grinding disk at 300 rpm for 6 h in a Dispermat AE mill from VMA Getzmann at room temperature and then the grinding beads are removed with a centrifuge. The mean grain diameter is measured with a Malvern Mastersizer laser diffraction particle size measuring instrument and found to be 0.239 m. 100 g of the diethylphosphinic salt/telomer/oligomer mixture obtained are introduced into a thermostatted duplex kneader from Flender Himmel (HKD-T06-D, equipped with a nitrogen connection) and heated to about 160 C. in an N.sub.2 counterflow (5 L/h) and at 100 rpm for 8 hours, then the reaction mixture is cooled down to room temperature with continuous kneading and kneaded for a further 2 hours. The polymeric flame retardant mixture is obtained in the form of fine granules. The yield is quantitative. Polymerization is demonstrated by measuring a GPC. The batch and analysis data, including the melt pump test and the flame retardancy properties, are listed in table 2. The ratio of dialkylphosphinic salt to telomer in the polymeric flame retardant mixture is the same as in the starting material.

EXAMPLE 2

[0269] Analogously to example 1, 200 g of DPS-1 are stirred into a mixture of 228 g of epsilon-caprolactone and 8.8 g of dispersing aid. The melt pump test and flame retardancy properties are good and comparable with example 1. The batch, analysis and test data are listed in table 2. The ratio of dialkylphosphinic salt to telomer in the polymeric flame retardant mixture is the same as in the starting material.

EXAMPLE 3

[0270] Analogously to example 2, DPS-2 is ground at 50 C. The melt pump test and flame retardancy properties are good and comparable with example 2. The batch, analysis and test data are listed in table 2. The ratio of dialkylphosphinic salt to telomer in the polymeric flame retardant mixture is the same as in the starting material.

EXAMPLE 4

[0271] Analogously to example 2, DPS-3 is ground at 100 C. The melt pump test and flame retardancy properties are good and comparable with example 2. The batch, analysis and test data are listed in table 2. The ratio of dialkylphosphinic salt to telomer in the polymeric flame retardant mixture is the same as in the starting material.

EXAMPLE 5

[0272] Analogously to example 2, DPS-4 is ground at 20 C. The melt pump test and flame retardancy properties are good and comparable with example 2. The batch, analysis and test data are listed in table 2. The ratio of dialkylphosphinic salt to telomer in the polymeric flame retardant mixture is the same as in the starting material.

EXAMPLE 6

[0273] Analogously to example 2, DPS-5 is ground at 20 C. The melt pump test and flame retardancy properties are good and comparable with example 2. The batch, analysis and test data are listed in table 2. The ratio of dialkylphosphinic salt to telomer in the polymeric flame retardant mixture is the same as in the starting material.

EXAMPLE 7

[0274] Analogously to example 2, DPS-6 is ground at 20 C. The melt pump test and flame retardancy properties are good and comparable with example 2. The batch, analysis and test data are listed in table 2. The ratio of dialkylphosphinic salt to telomer in the polymeric flame retardant mixture is the same as in the starting material.

EXAMPLE 8

[0275] Analogously to example 2, DPS-7 is ground at 20 C. The melt pump test and flame retardancy properties are good and comparable with example 2. The batch, analysis and test data are listed in table 2. The ratio of dialkylphosphinic salt to telomer in the polymeric flame retardant mixture is the same as in the starting material.

EXAMPLE 9

[0276] Analogously to example 2, DPS-8 is ground at 20 C. The melt pump test and flame retardancy properties are good and comparable with example 2. The batch, analysis and test data are listed in table 2. The ratio of dialkylphosphinic salt to telomer in the polymeric flame retardant mixture is the same as in the starting material.

EXAMPLE 10

[0277] Analogously to example 2, DPS-1 is ground for 2 hours. Polymerization is weaker than in example 2. The melt pump test and flame retardancy properties are good and comparable with example 2. The batch, analysis and test data are listed in table 2. The ratio of dialkylphosphinic salt to telomer in the polymeric flame retardant mixture is the same as in the starting material.

EXAMPLE 11

[0278] Analogously to example 2, 300 g of DPS-1 are ground with 800 g of grinding beads. Polymerization is weaker than in example 2. The melt pump test and flame retardancy properties are good and comparable with example 2. The batch, analysis and test data are listed in table 2. The ratio of dialkylphosphinic salt to telomer in the polymeric flame retardant mixture is the same as in the starting material.

EXAMPLE 12

[0279] DPS-1 (200 g) is stirred into 228 g of delta-valerolactone at room temperature. Then the grinding beads are added and grinding is effected with a grinding disk at 300 rpm for 10 h in a Dispermat AE mill from VMA Getzmann, beginning at room temperature and ending at about 160 C., and then the grinding beads are removed with a centrifuge. The mean grain diameter is measured with a Malvern Mastersizer laser diffraction particle size measuring instrument and found to be 0.201 m.

[0280] The polymeric flame retardant mixture is obtained in the form of fine granules. The yield is quantitative. Polymerization is demonstrated by measuring a GPC. The batch data, analysis data and test data, including the melt pump test and the flame retardancy properties, are listed in table 2.

[0281] The melt pump test and flame retardancy properties are good and comparable with example 2. The ratio of dialkylphosphinic salt to telomer in the polymeric flame retardant mixture is the same as in the starting material.

EXAMPLE 13

[0282] Analogously to example 2, 233 g of DPS-1 are ground with 173 g of gamma-butyrolactone and 700 g of grinding beads. Polymerization is weaker than in example 2. The melt pump test and flame retardancy properties are good and comparable with example 2. The batch, analysis and test data are listed in table 2. The ratio of dialkylphosphinic salt to telomer in the polymeric flame retardant mixture is the same as in the starting material.

EXAMPLE 14 (COMPARATIVE)

[0283] Analogously to example 2, aluminum hydroxide is ground. No effective polymerization takes place. Owing to its low molar mass (see table 2), the material cannot be processed to give a flame-retardant fiber and film polymer molding compound of the invention. The batch, analysis and test data are listed in table 2.

EXAMPLE 15 (COMPARATIVE)

[0284] 5% by weight of DPS-1, which, with a d.sub.50 of 2.5 m and a d.sub.95 of 8 m, is coarser than the diethylphosphinic salt of the invention or the mixture of diethylphosphinic salt and telomer of the invention, is processed to give a flame-retardant fiber and film polymer molding compound. The melt pump test leads to a significant rise in pressure (blockage). The material cannot be processed to give a flame-retardant fiber and film polymer molding compound of the invention. The test data are listed in table 2.

[0285] The positive properties of the polymeric flame retardant mixtures of the invention that were found in the examples were also obtained when a mixture of diethylphosphinic salt and propylhexylphosphinic salt (telomer) or a mixture of dipropylphosphinic salt and propylhexylphosphinic salt (telomer) was used.

TABLE-US-00004 TABLE 2 Grinding Starting Carrier Grinding Grinding Grinding material material Dispersant beads time temp. Example [g] Name [g] Name [g] Amount [h] [ C.] 1 DPS 1 150 epsilon- 200 1400 6 20 caprolactone 2 DPS 1 200 epsilon- 228 DSP 8.8 1400 6 20 caprolactone 3 DPS 2 200 epsilon- 228 DSP 8.8 1400 6 50 caprolactone 4 DPS 3 200 epsilon- 228 DSP 8.8 1400 6 100 caprolactone 5 DPS 4 200 epsilon- 228 DSP 8.8 1400 6 20 caprolactone 6 DPS 5 200 epsilon- 228 DSP 8.8 1400 6 20 caprolactone 7 DPS 6 200 epsilon- 228 DSP 8.8 1400 6 20 caprolactone 8 DPS 7 200 epsilon- 228 DSP 8.8 1400 6 20 caprolactone 9 DPS 8 200 epsilon- 228 DSP 8.8 1400 6 20 caprolactone 10 DPS 1 200 epsilon- 228 DSP 8.8 1400 2 20 caprolactone 11 DPS 1 300 epsilon- 228 DSP 8.8 800 6 20 caprolactone 12 DPS 1 200 delta-valero- 228 DSP 8.8 1400 10 20 lactone 13 DPS 1 233 gamma- 173 700 6 20 butyrolactone 14 ATH 200 epsilon- 228 DSP 8.8 1400 6 20 caprolactone 15 DPS 1 Grinding Product Particle Melt size Polymerization Molar mass n pump LOI d50 d95 temp. time Mn Mw Weight- test [% Example [m] [m] [ C.] [h] Process [g/mol] [g/mol] average [bar] O.sub.2] 1 0.24 0.72 162 6 1 9711 16894 148 57 29 2 0.24 0.78 160 6 1 9231 16154 142 51 31 3 0.24 0.90 142 6 1 8731 14569 128 60 30 4 0.30 0.91 163 6 1 8250 14229 125 55 30 5 0.23 0.71 156 6 1 9212 16411 144 60 30 6 0.20 0.73 161 6 1 9234 16020 140 58 31 7 0.21 0.70 157 6 1 9221 16358 143 55 32 8 0.28 0.81 161 6 1 9350 16406 144 53 32 9 0.24 0.77 160 6 1 9162 16580 145 51 32 10 0.50 2.60 164 6 1 2776 6434 56 60 29 11 1.12 3.13 161 6 1 3428 6378 56 66 29 12 0.20 0.71 161 10 2 9121 14055 140 59 29 13 0.23 0.67 160 6 1 about about 3 60 29 200 250 14 0.25 0.84 161 6 1 about about 2 72 20 230 250 15 130