Hydrolysis-stable and polymerizable acrylophosphonic acid

Details Hydrolysis-stable and polymerizable acrylophosphonic acid Hydrolysis-stable and polymerizable acrylophosphonic acid

2001-04-13

2004-03-23

Cain, Edward J. (Department: 1714)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C523S116000, C523S118000, C558S166000, C558S167000

Reexamination Certificate

active

06710149

ABSTRACT:

The present invention relates to polymerizable acrylophosphonic acids which have a high hydrolysis stability and are suitable in particular for preparing, or as components of, polymers, adhesives or other materials and mainly dental materials.
Polymerizable phosphonic acids are of polymer-chemical importance mainly as comonomers. They allow the preparation of organic polymers with high thermal stability, good adhesion properties, high ignition temperature and good solubility in polar solvents. For this purpose, numerous monomeric phosphonic acids with polymerizable vinyl, dienyl, allyl, or styryl groups have been synthetized and polymerized. An overview of phosphonic acids is given by Houben-Weyl, Methoden der Organischen Chemie, Vol. E 20 (2
nd
part), Georg Thieme Verlag, Stuttgart-New York 1987, p. 1300 et seq). Examples of such conventional polymerizable phosphonic acids are vinyl phosphonic acid, allylbenzene phosphonic acid, &agr;-aminoallyl phosphonic acid, phenylethene phosphonic acid, 1,3-butadiene or isoprene phosphonic acid, 4-vinylbenzene phosphonic acid or 2-(4-vinylphenyl)-ethane phosphonic acid.
Phosphonic acids in which the C═C group is bound to the phosphorus atom directly or via an oxygen atom, such as e.g. vinyl phosphonic acid or ethyl phosphonic acid monovinyl ester, show at most only a moderate tendency towards homopolymerization, so that only homopolymers with a low molecular weight are accessible.
High-molecular-weight polymerisates can on the other hand be obtained from (meth)acrylophosphonic acids or esters in which the (meth)acrylic group is not bound directly to the phosphorus, but via a hydrolysis-stable spacer group. Such (meth)acrylophosphonic acid derivatives are described for example in DE-B-27 11 234.
DE-A-32 10 775 discloses 2-acrylamido-2-methyl-propane phosphonic acid with the formula CH
2
═CH—CONH—C(CH
3
)
2
—CH
2
—P(═O)(OH)
2
as well as its use for preparing copolymerides.
DE-A-33 13 819 and JP 62-63314 (Chem. Abstr. 107 (1987), 41318f) disclose methacrylic acid-(2-phosphono-1,1-dimethylethylamine) of the formula CH
2
═C(CH
3
)—CONH—C(CH
3
)
2
—CH
2
—P(═O)(OH)
2
.
According to EP-B-0 089 654 and U.S. Pat. No. 4,650,591 acrylic acid-(2-phosphono-1,1-dimethylethylamine), also called 2-acrylamido-2-methylpropylhosphonic acid, is suitable as a corrosion inhibitor in the form of its homo- or copolymers.
DD-A-273 846 discloses adhesion promoters based on N-acyl-aminomethan-bisphosphonic acid derivatives.
These known (meth)acrylophosphonic acid derivatives are not stable in aqueous solution. Rather, they show, a hydrolytic clearage of the (meth)acrylic group which is even catalyzed by dissociated protons of the phosphonic acid group and thus accelerated.
The use of aqueous solutions is however advantageous or absolutely necessary in a whole series of applications of polymerizable phosphonic acids. This is the case e.g. in the preparation of low viscosity adhesives which are free from organic solvents, or in dental adhesives which lead to an optimal wetting of the moist dentine surfaces only in aqueous form.
DE 197 46 708 A1 discloses polymerizable acrylophosphonic acids which are hydrolysis-stable in an aqueous solution, have good adhesion properties, can be polymerized with conventional radical initiators and are therefore suitable as a component in particular of adhesives, molded articles, cements or composites and in particular dental materials. The acrylophosphonic acids show a good solubility, in the form of their carboxylic acid esters, in water and polar organic solvents, whereas in the form of carboxylic acids they are easily soluble in water but hardly soluble in organic solvents. The different dissolving behaviour of ester and acid can be disadvantageous in the case of aqueous materials. The hydrolysis of the carboxylic acid esters to produce free carboxylic acid and alcohol can significantly change the solubility of the monomers and thus lead to partial or complete precipitation of the phosphonic acid component and thus influence the properties of the material.
The object of the invention is the preparation of polymerizable acrylophosphonic acids which are practically completely hydrolysis-stable in the presence of water at room temperature.
Surprisingly, this object was achieved by acrylophosphonic acids of the following general formula (I)
in which R
1
, R
2
, R
3
, X, Y, Z and n have the following meanings:
R
1
=a linear or branched C
1
to C
10
alkylene or C
6
to C
14
arylene radical;
R
2
=hydrogen, a linear or branched C
1
to C
10
alkyl or C
6
to C
10
aryl radical;
Y=oxygen, sulphur, C
1
to C
8
alkylene or is absent;
n=1, 2, 3, 4, or 5;
where
X=CN, n=1 and Z=absent or
X=CONR
3
with
R
3
=hydrogen, a linear or branched C
1
to C
10
alkyl radical or a C
6
to C
10
aryl radical;
provided that
for n=1
Z=hydrogen or a linear or branched C
1
to C
10
alkyl radical or a phenyl radical; and
for n=2 to 5
Z=an aliphatic, aromatic or araliphatic, linear or branched hydrocarbon radical with 1 to 14 carbon atoms, substituted n times with the structure of formula (I) in brackets, when Z and R
3
may also be a part of a common ring, and when
the individual radicals may be substituted or unsubstituted.
The individual alkyl, aryl, alkylene, arylene, phenyl, phenylene and arylene alkylene radicals can be substituted by one or more substituents, such as Cl, Br, CH
3
O, OH, COOH, CN, ═O, ═S, ═NR
2
or —NR
3
—CO—C(═CH
2
)CH
2
—Y—R
1
—PO(OH)
2
.
The nitriles (X═CN) can be transformed into the amides (X═CONR
3
) and can therefore be regarded as their precursors.
Further, there are preferred definitions for the above mentioned variables of the formula (I) which, unless otherwise stated, can be chosen independently from each other and are as follows:
R
1
=a linear or branched C
1
to C
5
alkylene radical or phenylene;
R
2
=hydrogen or a linear C
1
to C
3
alkyl radical;
Y=oxygen or is absent;
X=CN or CONR
3
with
R
3
=hydrogen, a linear C
1
to C
6
alkyl radical, a phenyl radical or together with Z part of a six-membered ring;
n=1 or 2;
Z=hydrogen or a linear or branched C
1
to C
10
alkyl radical, a phenyl radical or together with R
3
part of a six-membered ring (for n=1); and
Z=a linear C
1
to C
10
alkylene radical or together with R
3
part of a six-membered ring (for n≧2).
Particularly preferred meanings which can also be chosen independently of each other are:
R
1
=a linear or branched C
1
to C
4
alkylene radical;
R
2
=hydrogen or a methyl radical;
Y=oxygen;
X=CONR
3
;
R
3
=hydrogen or a linear C
1
to C
5
alkyl radical;
Z=hydrogen or a linear C
1
to C
6
alkyl radical (for n=1); and
Z=a linear C
1
to C
5
alkylene radical (for n≧2).
The radicals R
1
, R
2
, R
3
and/or Y are preferably unsubstituted, the radical Z is preferably unsubstituted or substituted by ═O, ═S, ═NR
2
or —NR
3
—CO—C(═CH
2
)CH
2
—Y—R
1
—PO(OH)
2
.
Preferred compounds are those where at least one, more preferably all, of the variables of formula (I) have the preferred definitions described above, the formula (I) including all the stereoisomers possible through the named substituents and their mixtures, such as racemates.
The acrylophosphonic acids according to the invention of formula (I) (X═CN, Z is absent) can be prepared by reacting alkylphosphonic acid esters APE &ggr;-functionalized at the alkyl radical (R
2
=alkyl) with &agr;-halogen methylacryl nitrites (U=halogen, preferably Cl or Br) HMAN and subsequent elimination of the alkyl groups R
2
using methods known from organic chemistry for preparing C—C—, C—O— or C—S— bonds (cf. C. Weygand, G. Hilgetag, Organisch-chemische Experimentierkunst, Johann Ambrosius Bart Verlag, Leipzig 1970, pp. 963 et seq, 362 et seq, and 657 et seq). The protection groups technique is used for the two phosphonic

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