Mixtures Of At Least One Dialkylphosphinic Acid With At Least One Other Dialkylphosphinic Acid That Is Different Therefrom, Method For Production Thereof, And Use Thereof

Abstract

The invention relates to a mixture of at least one dialkylphosphinic acid of the formula (I)

##STR00001##

in which R.sup.1, R.sup.2 are the same or different and are each C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, C.sub.6-C.sub.18-aryl, C.sub.7-C.sub.18-alkylaryl, with at least one different dialkylphosphinic acid of the formula (II)

##STR00002##

in which R.sup.3, R.sup.4 are the same or different and are each C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, C.sub.6-C.sub.18-aryl and/or C.sub.7-C.sub.18-alkylaryl, with the proviso that at least one of the R.sup.3 and R.sup.4 radicals is different than R.sup.1 and R.sup.2.

Claims

1.-21. (canceled)

22. A flame-retardant thermoplastic or thermoset polymer molding composition or polymer molding, film, filament or fiber comprising 0.5 to 45% by weight of a mixture of at least one dialkylphosphinic acid of the formula (I) ##STR00005## wherein R.sup.1, R.sup.2 are the same or different and are C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, C.sub.6-C.sub.18-aryl or C.sub.7-C.sub.18-alkylaryl, with at least one different dialkylphosphinic acid of the formula (II) ##STR00006## wherein R.sup.3, R.sup.4 are the same or different and are C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, C.sub.6-C.sub.18-aryl or C.sub.7-C.sub.18-alkylaryl, with the proviso that at least one of the R.sup.3 and R.sup.4 radicals is different than R.sup.1 and R.sup.2, 0.5 to 99.5% by weight of thermoplastic or thermoset polymer or mixtures thereof, 0 to 55% by weight of additives and 0 to 55% by weight of filler or a reinforcing material, where the sum of the components is 100% by weight.

23. A flame-retardant thermoplastic or thermoset polymer molding composition or polymer molding, film, filament or fiber comprising 1 to 30% by weight of a mixture of at least one dialkylphosphinic acid of the formula (I) ##STR00007## wherein R.sup.1, R.sup.2 are the same or different and are C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, C.sub.6-C.sub.18-aryl or C.sub.7-C.sub.18-alkylaryl, with at least one different dialkylphosphinic acid of the formula (II) ##STR00008## wherein R.sup.3, R.sup.4 are the same or different and are C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, C.sub.6-C.sub.18-aryl or C.sub.7-C.sub.18-alkylaryl, with the proviso that at least one of the R.sup.3 and R.sup.4 radicals is different than R.sup.1 and R.sup.2, 10 to 95% by weight of thermoplastic or thermoset polymer or mixtures thereof, 2 to 30% by weight of additives and 2 to 30% by weight of filler ora reinforcing material, where the sum of the components is 100% by weight.

Description

EXAMPLE 1

[0112] According to EP-A-1544205, example 8, a diethylphosphinic acid metal salt solution is obtained from sodium hypophosphite by means of initiator and ethylene. Subsequent treatment of the product solution with dilute sulfuric acid, concentration, filtration and distillation at 184° C. (1 mbar) dive a yield of 94% of a mixture of diethylphosphinic acid (99.9% by weight) and butylethylphosphinic acid (0.01% by weight).

EXAMPLE 2

[0113] According to EP-A-1544205, example 8, a diethylphosphinic acid metal salt solution is obtained from sodium hypophosphite by means of initiator and ethylene. Treatment of the product solution with dilute sulfuric acid, concentration, filtration and distillation at 180-190° C. (1 mbar) give a yield of 92% of a mixture of diethylphosphinic acid (98% by weight) and butylethylphosphinic acid (2% by weight).

EXAMPLE 3

[0114] Diethylphosphinic acid is obtained analogously to EP-A-1544205, example 8, from sodium hypophosphite by means of initiator and ethylene, and is purified by means of subsequent distillation.

[0115] Butylethylphosphinic acid is synthesized by reaction of ethylphosphinic acid with butene analogously to WO-A-2009/010188. A mixture of diethylphosphinic acid and butylethylphosphinic acid in a weight ratio of 90:10 is obtained by mixing the two pure components.

EXAMPLE 4

[0116] In a manner corresponding to example 3, a mixture of diethylphosphinic acid and butylethylphosphinic acid in a weight ratio of 60:40 is obtained by mixing the two pure components.

EXAMPLE 5

[0117] In a manner corresponding to example 3, a mixture of diethylphosphinic acid and butylethylphosphinic acid in a weight ratio of 50:50 is obtained by mixing the two pure components.

[0118] General method for producing polymer moldings:

[0119] a) Preparation of Phosphorus-Modified Epoxy Resin [0120] A 2 l five-neck flask apparatus is initially charged with 1000 g of the epoxy resin (e.g. Beckopox EP 140). It is heated to 110° C. for one hour and volatile components are removed under reduced pressure. Thereafter, the reaction mixture is inertized with nitrogen and the temperature in the flask is increased to 170° C. 118 g of the mixture of the phosphorus compounds (selected from examples 1 to 5) are added in each case, while stirring under flowing nitrogen, and an exothermic reaction is observed. The resulting resin is yellow in color and free-flowing.

[0121] b) Production of Epoxy Resin Specimens [0122] 100 parts of the phosphorus-modified epoxy resin are mixed with one corresponding OH equivalent of phenol novolac (hydroxide equivalents 105 g/mol, melting point 85-95° C.) and heated to 150° C. The mixture is stirred until a homogeneous mixture has formed and is allowed to cool to 130° C. Then 0.03 part 2-phenylimidazole is added and the mixture is stirred once again for 5-10 min. Thereafter, the mixture is poured warm into a dish and cured at 140° C. for 2 h and at 200° C. for 2 h.

[0123] c) Production of Epoxy Resin Laminate [0124] 100 parts phosphorus-modified epoxy resin as per b) are added to 63 parts acetone and 27 parts Dowanol® PM, and the appropriate amount of phenol resin is added. The mixture is left to stir for 30 min. and 2-phenylimidazole is added. Thereafter, the mixture is filtered through a 400 μm sieve in order to remove excess resin particles. Then a woven glass fabric (7628 type, 203 g/m.sup.2) is immersed into the solution until complete wetting of the fabric has taken place. The wetted fabric is pulled out of the mixture and excess resin is removed. Thereafter, the wetted fabric is initially cured in stages in a drying, cabinet for a brief period at temperatures up to 165° C. and then fully cured in a heated press. The resin content of the cured laminates is 30-50%.

[0125] The thermal expansion of the molding produced, a laminate, is determined to ASTM E831-06.

EXAMPLE 6

[0126] According to the general method for producing a polymer molding, 100% of a bisphenol A resin is used to produce a laminate.

EXAMPLE 7

[0127] Diethylphosphinic acid is obtained analogously to patent EP-A-1544205, example 8, from sodium hypophosphite by means of initiator and ethylene, and is purified by means of subsequent distillation.

[0128] According to the general method for producing a polymer molding, a composition composed to 90% by weight of bisphenol A resin with hardener and catalyst and 10% by weight of diethylphosphinic acid is used to produce a molding.

EXAMPLE 8

[0129] Butylethylphosphinic acid is synthesized by reaction of ethylphosphinic acid with butene analogously to WO-A-2009/010188.

[0130] According to the general method for producing a polymer molding, a composition composed to 90% by weight of bisphenol A resin with hardener and catalyst and 10% by weight of butylethylphosphinic acid is used to produce a molding.

EXAMPLE 9

[0131] According to the general method for producing a polymer molding, a composition composed to 90% by weight of bisphenol A resin with hardener and catalyst and 10% by weight of the inventive mixture according to example 1 is used to produce a molding.

EXAMPLE 10

[0132] According to the general method for producing a polymer molding, a composition composed to 90% by weight of bisphenol A resin with hardener and catalyst and 10% by weight of the inventive mixture according to example 2 is used to produce a molding.

EXAMPLE 11

[0133] According to the general method for producing a polymer molding, a composition composed to 90% by weight of bisphenol A resin with hardener and catalyst and 10% by weight of the inventive mixture according to example 3 is used to produce a molding.

EXAMPLE 12

[0134] According to the general method for producing a polymer molding, a composition composed to 90% by weight of bisphenoi A resin with hardener and catalyst and 10% by weight of the inventive mixture according to example 4 is used to produce a molding.

EXAMPLE 13

[0135] According to the general method for producing a polymer molding, a composition composed to 90% by weight of bisphenol A resin with hardener and catalyst and 10% by weight of the inventive mixture according to example 5 is used to produce a molding.

[0136] The results are reproduced in the following table:

TABLE-US-00002 Mixture of Composition dialkylphosphinic acid of polymer of the formula (I)/ Coefficient of system/ dialkylphosphinic acid thermal expansion mixture of the formula (II) 0°-100° [% by wt./ [% by wt./ [ppm/° C.] Example % by wt.] % by wt.] Z X Y 6 100:0 69 20 7 7 90:10 100:10 70 21 8 8 90:10 0:100 71 20 7 9 90:10 99.9:0.1 65 18 5 10 90:10 98:2 63 17 5 11 90:10 90:10 60 16 5 12 90:10 60:40 58 14 4 13 90:10 50:50 56 13 4

[0137] Compared to the pure laminate (example 6), there is a decrease in the values for the coefficient of thermal expansion of the laminate comprising the inventive mixture of diethylphosphinic acid and butylethylphosphinic acid; thermal expansion is thus very low. An increase in the butylethylphosphinic acid content brings about a further improvement. The inventive products lead to lower expansion of the moldings produced and thus meet the demands on dimensional stability.