Process for preparing dialkylphosphinic acids

Details Process for preparing dialkylphosphinic acids Process for preparing dialkylphosphinic acids

1998-11-24

2001-10-09

Vollano, Jean F (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Phosphorus acids or salts thereof

Reexamination Certificate

active

06300516

ABSTRACT:

The invention relates to a process for preparing dialkylphosphinic acids and/or alkali metal salts thereof by reacting olefins with alkylphosphonous and/or hypophosphorous acid and/or alkali metal salts thereof and to the use of the compounds prepared by this process.
Owing to the difficulty of their industrial synthesis, dialkylphosphinic acids and their derivatives have been used in industrial areas of application to only a relatively small extent.
Specific secondary phosphines obtained by addition of branched or cyclic olefins to phosphine, after their oxidation to dialkylphosphinic acids, are used as selective extraction media for cobalt
ickel separation.
Mixtures of perfluoroalkylphosphinic acids and perfluoroalkylphosphonic acids are used as specific extraction media. They originate from the reaction of perfluoroalkyl iodides with elemental phosphorus after hydrolysis and subsequent oxidation (DE-A-2 233 941).
To prepare dialkylphosphinic acid derivatives, such as the total herbicide phosphinotricin, a complex synthesis route via the hydrolysis of methyldichlorophosphine to give methylphosphonous acid and subsequent esterification of the abovementioned acid to give a phosphonous ester must be selected, before the second phosphorus-carbon bond can be made under free-radical induction.
The use of dialkylphosphinic acid derivatives as flame retardants for polyesters (poly(ethylene terephthalate) and poly(butylene terephthalate)) is described (EP 0 699 708 A1).
The end products are synthesized in a complex manner using methyldichlorophosphine as organophosphorus starting material, the hydrolysis product methylphosphonous acid and the ester of this acid having to be prepared and isolated as intermediates.
To prepare dialkylphosphinic acids or derivatives thereof, such alkylphosphonous esters can be alkylated by &agr;-olefins at high temperatures under free-radical catalysis conditions. In the case of a reaction of alkylphosphonous acids under the same conditions, only the disproportionation products alkylphosphines and alkylphosphonic acids are obtained, however, whereas under mild conditions no reaction is observed.
U.S. Pat. No. 4,632,741 A1 describes a process for preparing mixtures of salts of alkylphosphonous and dialkylphosphinic acids, by reacting an olefin with a salt of hypophosphorous acid in the presence of a photoinitiator, using UV light.
U.S. Pat. No. 4,590,014 A1 describes a similar process in which the olefin is reacted with the alkali metal salt of hypophosphorous acid in the presence of a free-radical source (peroxide compound). However, the reaction finishes in this case as early as the stage of the alkylphosphonous acid.
According to Martinez et al. [Afinidad 53, 404 (1996)], in the above-described reaction, the yield of dialkylphosphinic acid is increased if said reaction is carried out in the presence of large amounts of sulfuric acid.
However, the above-described processes lead overall to unsatisfactory yields and in virtually all cases, in addition, to a mixture of reaction products, which must be worked up laboriously.
The object underlying the invention is therefore to provide a process for preparing dialkylphosphinic acids and/or alkali metal salts thereof by reacting olefins with alkylphosphonous and/or hypophosphorous acid and/or alkali metal salts thereof which avoids the abovementioned disadvantages and leads in a short time to high yields of dialkylphosphinic acids and/or alkali metal salts thereof.
This object is achieved by a process of the type described at the outset which comprises carrying out the reaction in the presence of a free-radical initiator.
Preferably, the olefins are unbranched or branched &agr;-olefins.
Preferably, the &agr;-olefins are ethylene, n-propylene, isopropylene, n-butene, isobutene, n-pentene, isopentene, n-hexene, isohexene, n-octene, isooctene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, n-eicosene and/or a 2,4,4-trimethylpentene isomeric mixture.
Suitable olefins are compounds of the formula
where R
1
-R
4
can be identical or different and are hydrogen, an alkyl group having from 1 to 18 carbon atoms, phenyl, benzyl or alkyl-substituted aromatics.
Likewise suitable are cycloolefins of the formula
in particular cyclopentene, cyclohexene, cyclooctene and cyclodecene.
Use can also be made of open-chain dienes of the formula
where R
5
-R
10
are identical or different and are hydrogen or a C
1
to C
6
alkyl group and R
11
is (CH
2
)
n
where n=0 to 6. Preference is given in this case to butadiene, isoprene and 1,5-hexadiene.
Cyclodienes which are preferred are 1,3-cyclopentadiene, dicyclopentadiene and 1,5-cyclooctadiene and also norbornadiene.
Preferably, as olefins, use is made of those having an internal double bond, cyclic or open-chain dienes and/or polyenes having from 4 to 20 carbon atoms.
Preferably, the olefins bear a functional group.
Preferably, the alkylphosphonous acid and/or alkali metal salts thereof are methylphosphonous acid or ethylphosphonous acid and/or alkali metal salts thereof.
Preferably, as free-radical initiators, use is made of azo compounds.
Preferably, the azo compounds are cationic and/or non-cationic azo compounds.
Preferably, as cationic azo compounds, use is made of 2,2′-azobis(2-amidinopropane) dihydrochloride or 2,2′-azobis(N,N′-dimethyleneisobutyramidine) dihydrochloride.
Preferably, as non-cationic azo compounds, use is made of azobis(isobutyronitrile), 4,4′-azobis(4-cyanopentanoic acid) or 2,2′-azobis(2-methylbutyronitrile).
Preferably, as free-radical initiators, use is also made of inorganic peroxide and/or organic peroxide free-radical initiators.
Preferably, as inorganic peroxide free-radical initiators, use is made of hydrogen peroxide, ammonium peroxodisulfate and/or potassium peroxodisulfate.
Preferably, as organic peroxide free-radical initiators, use is made of dibenzoyl peroxide, di-tert-butyl peroxide, and/or peracetic acid.
Preferably, the reaction is carried out in the presence of carboxylic acids.
Particularly preferably, the carboxylic acid is acetic acid.
Preferably, the reaction is carried out at a temperature of from 40 to 130° C.
Particularly preferably, the reaction is carried out at a temperature of from 60 to 100° C.
In particular, the process is preferably carried out at a temperature of from 80 to 95° C.
Preferably, the reaction is carried out in a pressure reactor. This is the case, in particular, if the boiling points of the olefins are below the reaction temperature.
The present invention also relates in particular to a process in which sodium hypophosphite is reacted with ethylene in the presence of a cationic or non-cationic free-radical initiator or in the presence of a peroxide free-radical initiator to give the sodium salt of diethylphosphinic acid as main product.
The invention also relates to the use of the dialkylphosphinic acids and/or alkali metal salts thereof obtained by the above-described process for preparing flame retardants.
The invention likewise relates to the use of the dialkylphosphinic acids and/or alkali metal salts thereof obtained by the above-described process for preparing flame retardants for thermoplastic polymers.
The invention likewise relates to the use of the dialkylphosphinic acids and/or alkali metal salts thereof obtained by the above-described process for preparing flame retardants for thermoplastic polymers such as poly(ethylene terephthalate), poly(butylene terephthalate), polystyrene or polyamides.
The dialkylphosphinic acids and/or alkali metal salts thereof obtained by the above-described process are also used as additives in polymeric compounds, as extraction media and surfactants.


REFERENCES:
patent: 2957931 (1960-10-01), Hamilton et al.
patent: 3488368 (1970-01-01), Spivack
patent: 3534127 (1970-10-01), Spivack
patent: 3563948 (1971-02-01), Spivack
patent: 3742096 (1973-06-01), Spivack
patent: 3912654 (1975-10-01), Heid et al.
patent: 3914345 (1975-10-01), Kleiner et al.
patent: 4036811 (1977-07-01), Noetzel
patent: 4208322 (1980-06-01), Sandler

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