Process for preparing ethylenedialkylphosphinic acids, esters and salts by means of acetylene and use thereof
View Patent ↗A process for preparing ethylenedialkylphosphinic acids, ethylenedialkylphosphinic esters and ethylenedialkylphosphinic salts, wherein a) a phosphinic acid source (I) is reacted with olefins (IV) in the presence of a catalyst A to give an alkylphosphonous acid, its salt or ester (II), b) the resultant alkylphosphonous acid, its salt or ester (II) is reacted with an acetylenic compound (V) in the presence of a catalyst B, to give the ethylenedialkylphosphinic acid derivative (III), and the catalyst A comprises transition metals, transition-metal compounds and/or catalyst systems which are composed of a transition metal and/or a transition-metal compound and at least one ligand, and the catalyst B comprises peroxide-forming compounds, peroxo compounds and/or azo compounds.
1. A process for preparing ethylenedialkylphosphinic acids, or salts or esters thereof comprising the steps of
a) reacting a phosphinic acid source (I)
with olefins IV
in the presence of a catalyst A to give an alkylphosphonous acid (II), or salt or ester thereof,
b) reacting the alkylphosphonous acid (II), or salt or ester thereof with at least one acetylenic compound (V)
in the presence of at least one catalyst B to give an ethylenedialkylphosphinic acid derivative (III)
where R 1 -R 6 are each H, R 11 -R 14 are each H,X is H, Ca, Mg, Al, Zn, Ti, Mg, Ce, Fe, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert- butyl, phenyl, 2-hydroxethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, allyl, glycerol or a combination thereof and the catalyst A is a transition metal or a transition metal compound catalyst system comprising of a transition metal or a transition metal compound and at least one ligand, and the catalyst B is peroxide-forming compound, peroxo compound, azo compound or a combination thereof 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-t-butyl peroxide, peroxodisulfuric acid, azodiisobutyronitrile, 2,2′-azobis(2-amidinopropane) dihydrochloride, 2,2′-azobis(N,N′-dimethyleneisobutyramidine) dihydrochloride and a combination thereof.
2. The process as claimed in claim 1 , wherein the ethylenedialkylphosphinic acid (III), or salt or ester thereof, obtained after step b) is reacted, in a step c), with a metal compound, a protonated nitrogen base or a combination thereof, wherein the metal compound is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na or K to yield ethylenedialkylphosphinic acid salts (III) of the metal compound, of the nitrogen base or a combination thereof.
3. The process as claimed in claim 1 , wherein the alkylphosphonous acid (II), salt or ester thereof, obtained after step a), the ethylenedialkylphosphinic acid (III), or salt or ester thereof, obtained after step b), or a combination thereof is esterified with an alkylene oxide or a branched, staturated or unsaturated, monohydric or polyhydric alcohol having a carbon chain length of C 1 -C 18 or a combination thereof, and the resulting alkylphosphonous ester (II) or ethylenedialkylphosphinic ester (III) formed is subjected to the further reaction step b).
4. The process as claimed in claim 1 , wherein the transition metal or the metal in the transition metal compound is selected from the seventh or eighth transition groups.
5. The process as claimed in claim 1 , wherein the transition metal or the metal in the transition metal compounds is rhodium, nickel, palladium, platinum, ruthenium or a combination thereof.