Mixtures composed of monocarboxy-functionalized dialkylphosphinic esters and of further components

Abstract

The invention relates to mixtures composed of dialkylphosphinic esters and of further components, which comprise A) from 98 to 100% by weight of monocarboxy-functionalized dialkylphosphinic esters of the formula (I)

Description

Claims

1. A mixture comprising: A) from 98 to 100% by weight of at least one monocarboxy-functionalized dialkylphosphinic ester of the formula (I)

2. The mixture as claimed in claim 1, comprising from 99.9995 to 100% by weight of the at least one monocarboxy-functionalized dialkylphosphinic esters ester of the formula (I) and from 0 to 0.0005% by weight of the at least one halogen.

3. The mixture as claimed in claim 1, wherein the at least one monocarboxy-functionalized dialkylphosphinic ester is methyl 3-(ethylhydroxyphosphinyl)propionate, 2-hydroxyethyl 3-(ethylhydroxyphosphinyl)propionate, 2,3-dihydroxypropyl 3-(ethylhydroxyphosphinyl)propionate, allyl 3-(ethylhydroxyphosphinyl)-2-methylpropionate, 4-hydroxybutyl 3-(ethylhydroxyphosphinyl)-2-methylpropionate, 6-hydroxyhexyl 3-(ethylhydroxyphosphinyl)propionate, 2-hydroxyethyl 3-(ethyl-n-butoxyphosphinyl)isobutyrate, butyl 3-(ethyl-n-butoxyphosphinyl)propionate, methyl 3-(ethylmethoxyphosphinyl)propionate, butyl 3-(propylhydroxyphosphinyl)propionate, 2-hydroxyethyl 3-(propylhydroxyphosphinyl)propionate, 2-hydroxypropyl 3-(propylhydroxyphosphinyl)propionate, 2-hydroxypropyl 3-(propylhydroxyphosphinyl)-2-methylpropionate, methyl 3-(propylhydroxyphosphinyl)propionate, 2-hydroxyethyl 3-(butylhydroxyphosphinyl)propionate, 3-hydroxypropyl 3-(hexylhydroxyphosphinyl)propionate, 2-hydroxyethyl 3-(ethylhydroxyphosphinyl)-2-methylbutyrate, 2-hydroxyethyl 3-(propylhydroxyphosphinyl)-2-methylbutyrate, 2-hydroxypropyl 3-(ethylhydroxyphosphinyl)-2-methylbutyrate, 2-hydroxypropyl 3-(propylhydroxyphosphinyl)-2-methylbutyrate, 2,3-dihydroxypropyl 3-(propylhydroxyphosphinyl)propionate, methyl 3-(ethylmethoxyphosphinyl)-2-methylbutyrate or a mixture thereof.

4. A process for preparation of a mixture as claimed in claim 1, comprising the step of reacting hypophosphorous acid or its salts a salt thereof (component C) of the formula II

5. The process as claimed in claim 4, wherein, in a step 1, component C is reacted in the presence of the at least one free-radical initiator with component E to give an alkylphosphorous acid and, in step 2, the resultant reaction solution is esterified with an alcohol M-OH to produce phosphorus ester in the resultant reaction mixture, and the phosphonous ester produced here is removed by distillation and, in a step 3, the resultant reaction mixture is reacted in the presence of the at least one free-radical initiator or of a basic initiator with component D to give the at least one monocarboxy-functionalized dialkylphosphinic ester.

6. The process as claimed in claim 4, wherein, in a step 1, component C is reacted in the presence of the at least free-radical initiator with component E to give an alkylphosphonous acid and, in step 2, the resultant reaction solution is esterified with an alcohol M-OH to produce phosphonous ester in the resultant reaction solution and the phosphonous ester is removed by distillation and, in a step 3, the resultant reaction mixture is reacted in the presence of the at least one free-radical initiator or of a basic initiator with component D′ to give the at least one monocarboxy-functionalized dialkylphosphinic ester, where X=alkyl, Y═H, and then, in a step 4, the dialkylphosphinic ester is esterified with an alcohol Y—OH at the carboxy function, giving a monocarboxy-functionalized dialkylphosphinic ester A.

7. The process as claimed in claim 6, wherein, in step 2, the alkylphosphonous acid is directly esterified with a linear or branched alcohol of the formula M-OH, where M is a linear or branched alkyl radical having from 1 to 10 carbon atoms.

8. The process as claimed in claim 7, wherein the alcohol M-OH is n-butanol, isobutanol, or ethylhexanol.

9. The process as claimed in claim 4, wherein component C is the ammonium or sodium salt of hypophosphorous acid.

10. The process as claimed in claim 4, wherein the at least one free radical initiator is a free-radical, anionic, cationic, or photochemical initiator.

11. The process as claimed in claim 4, wherein the at least one free radical initiator is a peroxide-forming compound, a peroxo compound, an azo compound or a mixture thereof.

12. The process as claimed in claim 4, wherein the at least one α,β-unsaturated carboxylic acid is acrylic acid, methyl acrylate, ethyl acrylate, methacrylic acid, hydroxyethyl acrylate, crotonic acid, ethyl crotonate, tiglic acid (trans-2,3-dimethylacrylic acid), (trans-)2-pentenoic acid or a mixture thereof.

13. The process as claimed in claim 4, wherein the at least one olefin (component E) is ethylene, propylene, n-butene, and/or isobutene, 1-hexene, 1-heptene, and/or 1-octene; allyl alcohol, allylamine, allylbenzene, allylanisole, styrene, α-methylstyrene, 4-methylstyrene, vinyl acetate or a mixture thereof.

14. The process as claimed in claim 4, wherein the reaction of component C with components D, E or both takes place at a temperature of from 50 to 150° C.

15. A process for preparation of a mixture as claimed in claim 1 comprising the steps of reacting component C, in a step 1, with a ketone to give 1-hydroxy-1-dialkylphosphinate, reacting the 1-hydroxy-1-dialkylphosphinate, in a step 2, in the presence of at least one free-radical initiator with component D, in a step 3, removing the ketone to form a resultant reaction mixture, and reacting the resultant reaction mixture, in a step 4, in the presence of the at least one free-radical initiator with component E.

16. A process for preparation of a mixture as claimed in claim 1, comprising the steps of reacting component C, in a step 1, with a ketone to give 1-hydroxy-1-dialkylphosphinate, reacting this the 1-hydroxy-1-dialkylphosphinate, in a step 2, in the presence of at least one free-radical initiator with component D′, in a step 3, removing the ketone to form a resultant reaction mixture, and reacting the resultant reaction mixture, in a step 4, in the presence of the at least one free-radical initiator with component E to form the monocarboxy-functionalized dialkylphosphinic acid, where Y═H, and reacting the monocarboxy-functionalized dialkylphosphinic acid with an alcohol YOH to give the monocarboxy-functionalized dialkylphosphinic ester.

17. A process for preparation of a mixture as claimed in claim 1, comprising the steps of reacting component C, in a step 1, with acetone to give 1-hydroxy-1-methylethylphosphinate, reacting the 1-hydroxy-1-methylethylphosphinate, in a step 2, in the presence of at least one free-radical initiator with component E, in a step 3, removing the acetone to form the a resultant reaction mixture, and reacting the resultant reaction mixture, in a step 4, in the presence of the at least one free-radical initiator with component D or D′.

18. The process as claimed in claim 17, wherein, after the reaction with component D′, the monocarboxy-functionalized dialkylphosphinic acid thus obtained, wherein Y═H is reacted with an alcohol YOH to give the monocarboxy-functionalized dialkylphosphinic ester.

19. A process of making a flame retardant or a flame retardant article comprising the step of adding a mixture as claimed in claim 1 to the flame retardant or flame retardant article during the manufacture of the flame retardant or the flame retardant article, wherein the flame retardant article is selected from the group consisting of flame-retardant molding compositions, flame-retardant moldings, flame-retardant films, flame-retardant filaments, and flame-retardant fibers.

20. The process as claimed in claim 19, wherein the flame retardant article comprises from 1 to 50% by weight of the mixture from 1 to 99% by weight of a polymer or a mixture of the same, from 0 to 60% by weight of additives, and from 0 to 60% by weight of filler, where the entirety of the components always amounts to 100% by weight.

21. The process as claimed in claim 4, wherein the at least one free radical initiator is selected from the group consisting of hydrogen peroxide, sodium peroxide, lithium peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, sodium peroxodisulfate, potassium peroxoborate, peracetic acid, benzoyl peroxide, di-tert-butyl peroxide, peroxodisulfuric acid, azodiisobutyronitrile, 2,2′-azobis(2-amidinopropane) dihydrochloride, 2,2′-azobis(N,N′-dimethyleneisobutyramidine) dihydrochloride and mixtures thereof.

22. A flame retardant or flame retardant article made in accordance with the process of claim 19.