Hydrolysis-stable and polymerizable acrylophosphonic acid...

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

2001-04-16

2002-02-26

Pezzuto, Helen L. (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S274000, C526S277000, C523S116000, C523S118000

Reexamination Certificate

active

06350839

ABSTRACT:

The present invention relates to polymerizable acrylophosphonic acid monoesters which have a high hydrolytic 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 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-methylpropylphosphonic 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 Al 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 the 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 hydrolysis-stable polymerisable acrylophosphonic acid derivatives which are easily soluble in water and in polar organic solvents and the solution behaviour of which is not changed by hydrolysis.
Surprisingly, this object was achieved by acrylophosphonic acid esters of the following general formula (I)
in which R
1
, R
2
, R
3
, X, Y, m and n, independently of each other, have the following meanings:
R
1
=a linear or branched C
1
to C
20
alkyl or C
6
to C
14
aryl radical;
R
2
=hydrogen, a linear or branched C
1
to C
5
alkyl or phenyl radical;
R
3
=a linear or branched C
1
to C
8
alkylene radical, phenylene or is absent;
Y=oxygen, C
1
to C
8
alkylene or is absent;
m=0 or 1;
n=1 or 2;
provided that Y=O, m=0 and R
3
=absent cannot be true at the same time and
further provided that
for m=1 and n=1
X=hydrogen or a linear or branched C
1
to C
5
alkyl radical or a C
6
to C
14
aryl radical;
for m=1 and n=2
X=a linear or branched C
1
to C
10
alkylene, C
6
to C
10
arylene, C
7
to C
20
arylalkylene radical or a chemical bond which links together two radicals with the structure of formula (I) in brackets.
The individual alkyl and alkylene radicals can be linear, branched or cyclic. In addition, the individual alkyl, aryl, alkylene, arylene, phenyl, phenylene and arylenealkylene radicals have one or more, preferably 1 to 2 substituents, such as Cl, Br, CH
3
, COOH, CN or preferably OH.
R
1
is preferably unsubstituted or substituted by one or more OH groups, preferably 1 or 2 OH groups. The remaining radicals are preferably not substituted.
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
10
alkyl or phenyl radical;
R
2
=hydrogen or a linear or branched C
1
to C
3
alkyl radical;
R
3
=a linear or branched C
1
to C
4
alkylene radical, phenylene or is absent;
Y=oxygen or is absent;
X=hydrogen or a linear or branched C
1
to C
3
alkyl radical (for m=1 and n=1); or
X=a linear or branched C
1
to C
6
alkylene radical, phenylene or a chemical bond which links together two radicals with the structure of formula (I) in brackets (for m=1 and n=2).
Meanings which are particularly preferred and likewise chosen independently of each other are:
R
1
=a linear or branched C
1
to C
4
alkyl radical which is unsubstituted or can be substituted by an OH group;
R
2
=hydrogen or a linear or branched C
1
to C
3
alkyl radical;
R=a linear or branched C
1
to C
4
alkylene radical, phenylene or is absent;
Y=oxygen or is absent.
Furthermore, acrylophosphonic acid monoesters are particularly preferred in which R
1
, R
2
, R
3
, Y and n have the above mentioned meanings and (i) m=0 or (ii) m=1, n=2 and
x=phenylene or a chemical bond which links together the two radicals with the structure of formula (I) in brackets.
Preferred compounds are those where at least one, particularly 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.
If m is equal to 0, the radicals X and R
2
are absent.
The acrylophosphonic acid monoesters (APME) according to the invention of the formula (I) can be prepared by partial hydrolysis of corresponding acrylophosphonic acid esters APE. For this, diluted caustic soda solution can be used, a silylation for example with trialkylsilanes is not necessary, so that the acrylophosphonic acid monoesters are more easily and economically accessible than comparable phosphonic acids.
Specifically, the reaction of 2-[4-(

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