Polymeric phosphinic acids and salts thereof

Details Polymeric phosphinic acids and salts thereof Polymeric phosphinic acids and salts thereof

2003-04-17

2004-04-27

Cheung, William (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

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Polymers from only ethylenic monomers or processes of...

C526S123100, C526S170000, C526S173000, C526S210000, C526S212000, C526S227000, C526S229000, C526S229500, C526S232100, C526S285000, C524S612000, C524S710000

Reexamination Certificate

active

06727335

ABSTRACT:

The present invention relates to novel polymeric phosphinic acids and their salts, to a process for their preparation, and to their use.
Phosphinic acids and their salts can be prepared by a variety of methods and have been widely described. For example, a comprehensive overview is found in Kosolapoff, Maier:
“Organic Phosphorus Compounds”
, Volume 6. Wiley-Interscience, 1973. The compounds known hitherto are mostly monomeric phosphinic acids, i.e. phosphinic acids which contain only one phosphinic acid group. Some diphosphinic acids and their salts are also known, for example ethane-1,2-diethylphosphinic acid (P. Mastalerz,
Roczniki Chem.
38, 61 (1964)).
Mention of polymeric phosphinic acids have so far been limited to coordination polymers in which monomeric phosphinic acids function as bridge ligands for metal ions. An overview of this group of products, known as polymeric metal phosphinates, is found in: B. P. Block,
Inorg. Macromol. Rev.,
1 (1970) 115-125.
The free-radical-initiated reaction of olefins with hypophosphorous acid is known and, as described in the as yet unpublished German patent application (file reference P19851618.5-44), gives the corresponding monomeric phosphinic acids.
The free-radical-initiated reaction of acetylenes with hypophosphorous acid has also been studied [Nifant'ev et al.,
Zh. Obshch. Khim
. (1986), 56(4) p. 773-781]; the reaction products obtained were merely mixtures of vinylphosphonous acids, divinylphosphinic acids and diphosphonous acids.
“Genuine” polymeric phosphinic acids, i.e. polymeric phosphinic acids with a structure based on covalent bonding and with phosphinic acid groupings in the repeat units, were not previously known.
The invention therefore provides polymeric phosphinic acids and their salts of the formula (I)
in which
X is hydrogen or a 1/m metal of valency m,
R
1
and R
2
are identical or different and are hydrogen, a carboxyl group, a carboxylic acid derivative, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, phenyl, benzyl or alkyl-substituted aromatics,
R
3
and R
4
are identical or different and are hydrogen or a vinyl group of the formula (VI)
 —CR
1
═CHR
2
  (VI)
in which R
1
and R
2
have the abovementioned meaning, and
{overscore (u)} is the average number of monomer units.
X is preferably a metal of groups IA, IIA, IIIA, IVA, VA, IIB, IVB, VIIB, VIIIB of the Periodic Table or is cerium.
The metal is preferably Li, Na, K, Mg, Ca, Sr, Ba, Al, Ge, Sn, Sb, Bi, Zn, Ti, Zr, Mn, Fe and/or Ce.
The metal is particularly preferably Na, Ca, Al and/or Zn.
X is preferably H.
Preferably, R
1
and R
2
are identical or different and are hydrogen or an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms.
Preferably, R
1
and R
2
are identical or different are and hydrogen or an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, where the substituents are one or more of the groups OH, CN or NH
2
.
Preferably, R
1
and R
2
are identical or different and are hydrogen or an alkyl group having from 1 to 4 carbon atoms and substitution by one or two OH groups.
Preferably, R
1
and R
2
are identical or different and are hydrogen or a carboxylic acid derivative.
Preferably, R
1
and R
2
are identical or different and are hydrogen or a carboxylic acid derivative of the formula COOR, where R is an alkyl group having from 1 to 4 carbon atoms.
R
3
and R
4
are preferably hydrogen.
Each of R
3
and R
4
is preferably a vinyl group of the formula —CR
1
═CHR
2
(VI), in which R
1
and R
2
have the abovementioned meanings.
R
3
is preferably H and R
4
is preferably a vinyl group of the formula —CR
1
═CHR
2
(VI), in which R
1
and R
2
have the abovementioned meanings.
R
3
is preferably a vinyl group of the formula —CR
1
═CHR
2
(VI), in which R
1
and R
2
have the abovementioned meanings and R
4
is H.
Each of R
1
and R
2
is preferably an identical or different alkyl group having 1 to 10 carbon atoms or is hydrogen, if at least one of the groups R
3
or R
4
is a vinyl group of the formula —CR
1
═CHR
2
.
The present invention in particular provides polymeric phosphinic acids and their salts of the formulae
The invention also provides a process for preparing polymeric phosphinic acids and their salts of the formula (I) which comprises reacting hypophosphorous acid and/or its alkali metal salts with acetylenes of the formula (II)
R
1
—C≡C—R
2
  (II)
in which R
1
and R
2
are identical or different and are hydrogen, a carboxyl group, a carboxylic acid derivative, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, phenyl, benzyl or alkyl-substituted aromatics.
Preference is given to reacting alkali metal salts of hypophosphorous acid with acetylenes of the formula (II) and then reacting the resultant alkali metal salts of the polymeric phosphinic acid with at least one metal compound of groups IA, IIA, IIIA, IVA, VA, IIB, IVB, VIIB, VIIIB of the Periodic Table, or with a cerium compound. This process therefore includes the conversion of a first alkali metal salt of the polymeric phosphinic acid into another alkali metal salt of the polymeric phosphinic acid.
Preference is given to reacting the hypophosphorous acid with acetylenes of the formula (II) and then reacting the resultant polymeric phosphinic acids with at least one metal compound of groups IA, IIA, IIIA, IVA, VA, IIB, IVB, VIIB, VIIIB of the Periodic Table, or with a cerium compound.
The metal compound is preferably a compound of Li, K, Na, Mg, Ca, Sr, Ba, Al, Ge, Sn, Sb, Bi, Zn, Ti, Zr, Mn, Fe and/or Ce.
Preference is given to reacting alkali metal salts of hypophosphorous acid with acetylenes of the formula (II) and then reacting the resultant alkali metal salts of the polymeric phosphinic acid with an acid to give the polymeric phosphinic acid. The resultant polymeric phosphinic acid may then be subjected to one or more of the abovementioned process steps.
There are therefore various ways of modifying the variable X in formula (I) as formulated above. If, for example, a starting material used for the reaction described above with acetylenes is readily obtainable alkali metal salts of hypophosphorous acid, the corresponding polymeric alkali metal phosphinates are produced, for example where X=Li, Na or K in formula (I). If hypophosphorous acid is used as a starting material, the free polyphosphinic acids are produced, where X=H in formula (I). The latter may also be obtained by acidifying the alkali metal phosphinates.
Using common precipitation and salt interchange reactions and starting from the alkali metal salts of the polyphosphinic acids or from the free polyphosphinic acids, it is possible to obtain polyphosphinic acid salts of a wide variety of metals, for example those of the alkaline earth metals, of the metals in main groups II to V, and also of transition group metals.
It is preferable to use from 0.6 to 1.5 mol of acetylene of the formula (II) per mole of hypophosphorous acid or of its alkali metal salt.
It is preferable to carry out the reaction in the presence of a free-radical initiator.
An overview of compounds of this type and their mode of operation is found, for example, in:
Houben
-
Weyl
, Supplementary Volume 20, Section entitled
“Polymerisation durch radikalische Initiierung” [Free
-
radical
-
initiated polymerization]
, pp. 15-74.
Preference is given to the use of azo compounds as free-radical-initiators.
The azo compounds used are preferably cationic and/or noncationic azo compounds.
The cationic azo compounds used are preferably comprise 2,2′-azobis(2-amidinopropane) dihydrochloride or 2,2′-azobis(N,N′-dimethyleneisobutyramidine) dihydrochloride.
The noncationic azo compounds used are preferably azobis(isobutyronitrile), 4,4′-azobis(4-cyanopentanoic acid) or 2,2′-azobis(2-methylbutyronitrile).
The free-radical initiators used are preferably inorganic peroxidic and/or organic peroxidic free-radical initiators.
The inorganic perox

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