CA2250333A1 - Hydrolysis-stable and polymerizable acrylphosphonic acids - Google Patents

Hydrolysis-stable and polymerizable acrylphosphonic acids Download PDF

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CA2250333A1
CA2250333A1 CA002250333A CA2250333A CA2250333A1 CA 2250333 A1 CA2250333 A1 CA 2250333A1 CA 002250333 A CA002250333 A CA 002250333A CA 2250333 A CA2250333 A CA 2250333A CA 2250333 A1 CA2250333 A1 CA 2250333A1
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acrylphosphonic
acid
dental material
meth
acrylate
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Norbert Prof. Dr. Moszner
Frank Dr. Zeuner
Volker Dr. Rheinberger
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Ivoclar AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3826—Acyclic unsaturated acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3839—Polyphosphonic acids
    • C07F9/386—Polyphosphonic acids containing hydroxy substituents in the hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3882—Arylalkanephosphonic acids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Biochemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
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  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Dental Preparations (AREA)

Abstract

Hydrolysis-stable and polymerizable acrylphosphonic acids are described which are particularly suitable as a component of dental adhesives owing to their adhesion-promoting properties.

Description

CA 022~0333 1998-10-1~

HydrolYsis-stable and PolYmerizable acrYlphosphonic acids The present invention relates to polymerizable acrylphosphonic acids which have a high degree of hydrolytic stability and are suitable in particular for the preparation or as components of polymers, adhesives or other materials and in particular of 5 dental materials.

Polymerizable phosphonic acids are of importance in polymer chemistry above all as comonomers, and they allow the preparation of organic polymers in which thermal stability, adhesive 10 properties, flammability and solubility in polar solvents are improved. To this end, numerous monomeric phosphonic acids having polymerizable vinyl, dienyl, allyl or styryl groups were synthesized and polymerized. An overview of phosphonic acids is given by Houben-Weyl, Methoden der Organischen Chemie, Volume E
15 20, (2nd part), Georg Thieme Verlag, Stuttgart-New York 1987, page 1300 et seq. Examples of such conventional polymerizable phosphonic acids are vinylphosphonic acid, allylbenzenephosphonic acid, ~-aminoallylphosphonic acid, phenylethenephosphonic acid, 1,3-butadiene- or isoprenephosphonic acid, 4-20 vinylbenzenephosphonic acid or 2-(4-vinylphenyl)-ethane phosphonic acid.

However, phosphonic acids in which the double bond is bound to the phosphorus atom directly or via an oxygen atom, such as 25 vinylphosphonic acid or ethylphosphonic acid monovinyl ester, exhibit an only moderate tendency to homopolymerization.
Therefore, only homopolymers with a small molecular weight can be obtained from them. In contrast, high-molecular-weight polymerizates can be obtained from (meth)acrylphosphonic acids 30 or esters in which the (meth)acrylic group is not bound directly to the phosphorus. Known (meth)acrylphosphonic acid derivatives are e.g. the phenylphosphonic acid-mono-(methacryloyloxyethyl)-esters of formula (a) or tert-butylphosphonic acid mono[1,3-di(methacryloyloxy)propan-2-yl)-esters of formula (b), described CA 022~0333 1998-10-1~

in DE-B-27 11 234. O O

O ~ C-F ~ ~ ~

(a) I (b) Moreover, acrylic acid-(2-phosphono-1,1-dimethylethylamine) is known from DE-A-32 10 775 and methacrylic acid-(2-phosphono-1,1-dimethylethylamine) of the formula (c) is known from DE-A-33 13 10 819 and JP 62-63314 (Chem. Abstr. 107 (1987), 41318f).

~ ~ H2- F-O~ (R = H or CH3) (c) P~ C~3 OH

Acrylic acid-(2-phosphono-1,1-dimethylethylamine), also called 20 acrylamido-2-methylpropanephosphonic acid, is used in the form of its homo- or copolymers as corrosion inhibitors (cf. EP-B-89 654 and US-A-4 650 591).

Finally, N-acryl-aminomethanebisphosphonic acid of the formula 25 (d) is also described in DD-A-273 846.

Il P(O(OH)2 NH-¢H (d) P(C(OHj All of these known (meth)acrylphosphonic acid derivatives are, however, not stable in aqueous solution. Rather, a hydrolytic cleavage of the (meth)acrylic group takes place which is even catalysed by dissociated protons of the phosphonic acid group and 35 thereby accelerated.

CA 022~0333 1998-10-1 However, the use of aqueous solutions is advantageous or absolutely necessary in a whole series of applications of polymerizable phosphonic acids. This is e.g. the case in the preparation of low-viscosity adhesives which are free of organic 5 solvents, or in that of dental adhesives which result in an optimum wetting of the moist dentine surface only in aqueous form.

It is therefore the object of the invention to make available 10 polymerizable acrylphosphonic acids which are hydrolysis-stable in aqueous solution and have good adhesion properties, can be polymerized using conventional radical initiators and are therefore suitable as a component of in particular adhesives, shaped bodies, cements or composites and above all of dental 15 materials.

This object is surprisingly achieved by the hydrolysis-stable and polymerizable acrylphosphonic acids according to Claims 1 and 2.

20 The subject of the present invention is also the process for the preparation of the acrylphosphonic acids according to Claim 3, the use thereof according to Claims 4 to 6, the dental material according to Claims 7 and 8, and polymers and copolymers of the acrylphosphonic acids according to Claim 9.
The acrylphosphonic acids according to the invention are compounds of the following general formula (I), stereoisomers thereof and mixtures of such stereoisomers _ ~ _ ~/\C--OR
Y O
X ¦ R- (I) C~=P-OH
1H - n CA 022~0333 1998-10-1 where Rl, R2, R3, X, Y and n, unless stated otherwise, independently of one another have the following meanings:

Rl = hydrogen, Cl to C10 alkyl or C6 to C~O aryl, R2 = hydrogen, fluorine, Cl to C5 alkyl or phenyl, R3 = Cl to C8 alkylene, phenylene or is absent, Y = oxygen, sulphur, C~ to C8 alkylene or is absent, n = 1 or 2, and with the proviso that (a) for n = 1 X = hydrogen, fluorine, C~ to C5 alkyl or C6 to C~2 aryl, and (b) for n = 2 X = C~ to C10 alkylene, C6 to C~O arylene, C7 to C20 arylenalkylene or is absent.

20 The individual alkyl and alkylene radicals can be straight-chain, branched or cyclic. Moreover, the individual alkyl, aryl, alkylene, arylene, phenyl, phenylene and arylenalkylene radicals can bear one or more substituents, such as Cl, Br, CH3, C2H5, CH30, OH, COOH, CN or NO2.
There also exist for the above-mentioned variables of the formula (I) preferred definitions which, unless otherwise stated, can be chosen independently of one another and are as follows:

30 Rl = hydrogen, Cl to C5 alkyl or phenyl, R2 = hydrogen, fluorine or C~ to C3 alkyl, R3 = C~ to C3 alkylene, phenylene or is absent, Y = oxygen, C~ to C3 alkylene or is absent, n = 1 or 2, CA 022~0333 1998-10-1 and with the proviso that (a) for n = 1 X = hydrogen, fluorine, Cl to C3 alkyl or phenyl, and (b) for n = 2 X = C~ to C6 alkylene, phenylene or is absent.

Preferred compounds are therefore those in which at least one of 10 the variables of the formula (I) has the above-described preferred definition, the formula (I) including all stereoisomers made possible by the mentioned substituents and their mixtures, such as racemates.

15 The acrylphosphonic acids according to the invention of the formula (I) can be prepared by reaction of a-halomethylacrylic acid esters of the formula (II) with protected mono- or difunctional phosphonic acid esters of the formula (III) and cleavage of the protective groups. In the formulae (II) and (III) 20 U is halogen, SG is protective group and the other variables are as defined above for formula (I). This reaction can be illustrated by the following general reaction equation which is followed by a concrete example.

~C--ORt '' .I 11 X ~ ~ I -n UH I -3 I r, ~ C_o.~l ~ X
I ~ O (+ cleavage ~

OSG n C=P-O~ n C! i (III) (II) (I) CA 022~0333 1998-10-1 Concrete examPle:

C Hs-O r 3r C ~ I ~ ~ cH_p,OC2Hs +HsC20 0 0 ~C2Hs H H
-2 HBr (+ cleavage ~ of SG) ~ ~CH--P(OH)~

C :i, C H2 I~=o c=r CC2Hc CC~Hc The reaction can be conducted by using the methods known from 20 organic chemistry for forming C-C, C-O or C-S bonds (cf. C.
Weygand, G. Hilgetag, Organisch-chemische Experimentierkunst, Johann Ambrosius Bart Verlag, Leipzig 1970, pages 963 et seq., 362 et seq. and 657 et seq.).

25 Used as protective groups (SG) are customary protective groups for phosphoric acid groups, such as ester groups, in particular SG is ethyl. After the reaction has taken place, these are split off according to conventional processes, in order to liberate the acrylphosphonic acids of the formula (I). The hydrolytic 30 cleavage of the protective groups SG is effected in particular by silylation with trialkylsilanes, e.g. trimethylsilyl chloride mixed with sodium iodide or bromide, and subsequent reaction with alcohols or water (cf. S. Freeman, J. Chem. Soc., Perkin Trans, 2 (1991) 263).

The ~-halomethylacrylic acid esters (II) used as starting materials can be obtained e.g. by reaction of the corresponding acrylic acid esters with formaldehyde in the presence of 1,4-diazabicyclo[2,2,2]octane (DABCO) and subsequent halogenation 5 with inorganic acid chlorides, such as SOClz, PCl3 or PBr3 (cf.
L.J. Mathias et al., Macromolecules 20 (1987) 2039, 2326, J.
Polym. Sci.: Part A: Polym. Chem. 32 tl994) 2937), and this reaction is illustrated by the following equation and a concrete example:
1R--o H~ 1R--O -rOH 1R--O U

O~ o~ - P(OH)3 (U = Br or Cl) (II) Concrete example:
C2Hs-O +H'C O C2H5-O OH p~3 C2Hs-O r Br O ~ H (CABCO) ~ - P(OH~
Suitable protected mono- or difunctional phosphonic acid esters (III) can be obtained by different methods. A particularly suitable method proceeds via the Michaelis-Arbusow reaction for the preparation of alkylphosphonic acid esters (cf. G.M.
25 Kosolapoff, Org. Reactions 6 (1951) 273). In this process, trialkyl phosphites, e.g. triethyl phosphite, and haloalkanes are reacted in accordance with the equations below, in which the Y-H
group must also be protected where necessary.

H H
y ~P--OC2Hs t R2 Br C2Hs ~3 C2HsO Br O=P-OS~
- -n OSG ~n (SG =C~H~) (III) CA 022~0333 1998-10-1 Concrete examPle:

C2HsO OH
P--OC2 H; C H2 C2H;O - Br-C2Hs ¢H2 B r--C H2--C H2--OH O=P--OC2 Hs Arylphosphonic acids can be obtained e.g. by Friedel-Crafts 10 reaction of aromatic hydrocarbons with phosphorus trichloride in the presence of aluminium trichloride, chlorination of the formed dichlorophosphine to tetrachlorophosphine and subsequent hydrolysis to the phosphonic acid (cf. G.M. Kosolapoff, Org.
Reactions 6 (1951) 273).
Furthermore, protected hydroxyalkylphosphonic acid esters (Y-H
= OH) where R3 = absent can be prepared by adding dialkyl phosphites with base catalysis to mono- or difunctional aldehydes or ketones analogously to the process according to F. Texier-20 Boullet, A. Foucaud, Synthesis, 1982, 916. This type of reactionand a concrete example thereof are shown by the following reaction equations:
H
O
C2H5O~"O O -Br-C2Hs C2HaO' + X ll ~ ' C=P-OSG
(SG=C2Hc) -n Concrete examPle:

C2HsO'P'OH ~~ ~ O-p-oc2Hs OC2H;

Examples of the acrylphosphonic acids according to the in~ention of formula (I) are inter alia:
HO O ~ - O O ~
~ e (~H?2 ~ o(OH)z ~ I (OH)2 ~ ~/\o(~H)2 r~~ --e(OHj2 ~ ~ --e(OH)~

O O ~ HO r O

o~ o o~ ~

HO O~ rO O~
o~ e(OH)~~ o(OH)2 ~/ ~
HO rO~ ~O rO~
0 ~ P(OH)2 ~ lo(OH)2 0~ 0 HO~ Pl (oH)2 r ~ lo(OH)2 r /e~~H)2 ~ / IP! ~OH)2 o~\ O ~ F O

CA 022~0333 1998-10-15 - 1~ - F
HoO~ ~1 (OH)2 ~--~~ ll (OH)2 o~ P(oH)2 HO~ I o(OH)2 ~ ~ F(OH)2 ~~ F o(OH)2 (HO~2P--CH~--CH--F(OH~2 (HO)2P--CH- <~--CH--P~OH)2 CH, CH,~ CH- CH2~=
Cl=O O=C C=O O=C
OC2H~ OC2H~ OH OH

~HO)2P---ICH--~CH,)~ Cl I--P(OH)2 (HO)2P--CH--(CH2)--CH--P(OH)2 ~0 0 0 0 =CH2 CH2~=~ CH2 CH2~=
C=O O=C C=O O=C
OC2H~ OC2H5 Otl OH

(HO)CP--Clt{;H--P(oH)2 (HO)2P--CH~H--P(OH32 '~ 1~ 1~ ~
C H2 C H2~= C H2 C H2~=
!CO OC ICO O!C
OC2H~ OC2Hs OH OH

. . , ,,, . .. ,.. , ~

CA 022~0333 1998-10-1~

Due to the presence of polymerizable groups the acrylphosphonic acids according to the invention are suitable as starting materials for the preparation of polymers and copolymers. They can be homopolymerized using the known methods of radical 5 polymerization or copolymerized e.g. with suitable comonomers.

In order to carry out the polymerization, the known radical initiators (cf. Encyclopedia of Polymer Science and Engineering, Vol. 13, Wiley-Interscience Publisher, New York 1988, 754 et 10 seq.) can be used. Suitable in particular are azo compounds, such as azobis(isobutyronitrile) (AIBN) or azobis(4-cyanovaleric acid), or peroxides, such as dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroctoate, tert-butyl perbenzoate or di-(tert-butyl)peroxide.
Benzpinacol and 2,2'-dialkylbenzpinacols are also suitable as initiators for the hot curing.

Furthermore, photoinitiators (cf J.P. Fouassier, J.F. Rabek 20 (publisher), Radiation Curing in Polymer Science and Technology, Vol. II, Elsevier Applied Science, London and New York 1993) can also be used for polymerization with W light or visible-wavelength light, such as benzoin ethers, dialkylbenzil ketals, dialkoxyacetophenones, acyl phosphine oxides, ~-diketones, such 25 as 9,10-phenanthrenequinone, diacetyl, furil, anisil, 4,4'-dichlorobenzil and 4,4'-dialkoxybenzil, and camphor quinone.

The acrylphosphonic acids can be used in particular as a components of adhesives, of cements, of composites and shaped 30 bodies and preferably of dental materials. It is possible that they are present in at least partially polymerized form. Other components with which the acrylphosphonic acids can be combined are mentioned below.

35 The acrylphosphonic acids according to the invention can be polymerized alone or mixed with conventional radically CA 022~0333 1998-10-1 polymerizable comonomers, in particular with difunctional crosslinking monomers. Suitable for the preparation of adhesives or dental materials are above all crosslinking bi- or polyfunctional acrylates or methacrylates, such as bisphenol-A-5 di(meth)acrylate, the addition product, called bis-GMA, of methacrylic acid and bisphenol-A-diglycidyl ether; the addition product, called UDMA, of hydroxyethyl methacrylate and 2,2,4-trimethylhexamethylene diisocyanate; di-, tri- or tetraethylene glycol di(meth)acrylate; decanediol di(meth)acrylate;
10 trimethylolpropane tri(meth)acrylate and pentaerythritol tetra(meth)acrylate. The compounds butanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate and 1,12-dodecanediol di(meth)acrylate, which can be obtained by esterification of (meth)acrylic acid with the corresponding diols, are also 15 suitable.

Moreover, the acrylphosphonic acids according to the invention or mixtures thereof with other radically polymerizable comonomers can be filled with organic or inorganic particles or fibres in 20 order to improve the mechanical properties. Preferred inorganic particulate fillers are amorphous spherical materials based on mixed oxides of SiOz, ZrO2 and/or TiO2, microfine fillers such as pyrogenic silica or precipitated silica, and macro- or mini-fillers, such as quartz powder, glass ceramic powder or glass 25 powder having an average particle size of 0.01 to 5 ~m. Finally, X-ray-opaque fillers, such as ytterbium trifluoride, or glass fibres, polyamide fibres or carbon fibres can also be used.

If necessary, further components can be added to the 30 acrylphosphonic acids, above all solvents, such as water, ethyl acetate, acetone, ethanol or mixtures thereof, and stabilizers, W absorbers, dyes, pigments or lubricants.

The acrylphosphonic acids according to the invention are suitable 35 in particular as a component of dental materials, such as fixing cements and filling composites and above all dental adhesives.

CA 022~0333 1998-10-1~

Such materials are characterized by very good adhesion to different substrates, such as tooth dentine and metallic substrates, which can be attributed to the acrylphosphonic acids used. It is assumed that the acrylphosphonic acids form ionic 5 and/or complex compounds with the calcium ions of the tooth dentine or with the metal ions of metallic substrates. These result in a greater adhesion than would be possible on the basis of simple dipole-dipole or van der Waals' interaction.

10 The surprisingly high hydrolytic stability of the acrylphosphonic acids also endows the materials according to the invention with a very good hydrolytic stability. This is true both for the unpolymerized and the polymerized material. A high hydrolytic stability is naturally of particular importance to those 15 materials which are permanently exposed to aqueous media, as is precisely the case with dental materials which are planned to reside in the oral cavity for a relatively long time.

Preferred dental materials according to the invention contain the 20 following components (a), (b), (c), (d) and/or (e):

(a) 1 to 99 wt.%, preferably 10 to 80 wt.% and particularly preferably 20 to 70 wt.% acrylphosphonic acids according to the invention, (b) 0.01 to 5 wt.% and preferably 0.1 to 2.0 wt.% radical initiator, (c) 0 to 80 wt.%, preferably 0 to 60 wt.% and particularly 30preferably 0 to 50 wt.% radically polymerizable comonomers, (d) 0 to 95 wt.%, preferably 0 to 80 wt.% and particularly preferably 0 to 70 wt.% solvent, CA 022~0333 l998- lO- l~

(e) 0 to 90 wt.%, particularly preferably, depending on the application, 0 to 20 wt.% (adhesive), 20 to 60 wt.%
(cement) and 60 to 85 wt.% (filling composite) filler.

5 The invention is explained in more detail below with reference to examples.

ExamPles 10 Example 1 1st staqe: 2- r 3-(diethoxyphosphoryl)-2-oxa-propyll-acrylic acid ethyl ester (1) 7.45 g (50 mmol) a-chloromethylacrylic acid ethyl ester were 15 added at room temperature with stirring to a solution of 8.4 g (50 mmol) hydroxymethylphosphonic acid diethyl ester, which is - easily obtainable by reacting diethyl phosphite with paraformaldehyde, 5.05 g (50 mmol) triethylamine (TEA) and 0.01 g phenothiazine (stabilizer) in 40 ml absolute tetrahydrofuran 20 (THF). After 30 minutes' stirring at room temperature, the mixture was heated under reflux for 16 hours. After cooling to room temperature, the formed precipitate of triethylammonium chloride was filtered off. The filtrate was diluted with 150 ml water, set to a pH value of ca. 5 to 7 with 2N hydrochloric acid 25 and extracted repeatedly with diethyl ether. After drying over anhydrous NazSO4, the extract was concentrated in a rotary evaporator, dried under a medium vacuum and finally distilled by fractionation. 10.8 g [b.p.: 120-125 C (0.007 mbar)] of a colourless liquid were obtained (77 % yield).
Elemental analysis:

CllH2lO6P Calc.: C 47.14 H 7.55 (280.26) Found: C 47.58 H 7.87 CA 022~0333 1998-10-1 IR (KBr, cm ): 780 (w), 818 (w), 877 (w), 967 (s), 1029 (s,sh), 1112 (s), 1176 (m), 1261 (s), 1306 (m), 1392 (m,sh), 1446 (w), 1719 (s), 2908 (w) and 2984 (m).

5 lH-NMR (300 MHz, CDCl~, ppm): 1.29-1.42 (m, 9H, CH3), 3.80 (d, 2H, CH2-P), 4.10-4.26 (m, 6H, CH2-CH3), 4.34 (s, 2H,CH2-C=CH2), 5.90 and 6.33 (s, 2xlH, C=CH2).

C-NMR (75 MHz, CDCl~, ppm): 14.20 and 16.47 (CH31), 60.78, 10 62.50, 63.68, 65.89 and 71.38 (all CH2t), 126.66 (CH2=Ct), 136.64 (CH2=C(-)) and 165.51 (C=O(-)).

3lP-NMR (121.5 MHz, CDCll, Ppm): 43Ø
~5 2nd staqe: 2- r 3-(dihYdroxyPhosPhorYl)-oxa-propyll-acrylic acid ethyl ester (2) O ~ O ~ P(OH)2 (2) 16.8 g (110 mmol) trimethylsilyl bromide were added dropwise to a solution of 14.0 g (50 mmol) of compound (1) and 0.01 g hydroquinone monomethyl ether (MEHQ, stabilizer) in 30 ml 25 absolute methylene chloride, and the mixture was stirred for 90 minutes under reflux. The mixture was then concentrated in a rotary evaporator, and the obtained residue was stirred for 2 hours after being taken up in 50 ml methanol. After treating the slightly reddish solution with activated charcoal, the solution 30 was concentrated in vacuo and then dried under a medium vacuum until the weight was constant. 9.1 g (81 % yield) of a viscous oil remained which had a purity of 98 % determined by means of HPLC.

CA 022~0333 1998-10-1 Elemental analYsis:

C7H13O6P Calc.: C 37.51 H 5.85 (224.15) Found: C 37.26 H 6.87 IR (KBr, cm ): 684 (w), 778 (w), 820 (m), 861 (m), 970 (s), 1020 (s), 1112 (s), 1182 (s,sh), 1309 (s,sh), 1405 (m,sh), 1466 (m,sh), 1632 (m), 1713 (s), 2324 (b) and 2600-3500 (b).

10 H-NMR (300 MHz, acetone-d~, ppm): 0.32 (ca. 1 % silyl compound), 1.28 (t, 3H, CH3), 3.86 (d, 2H, PCH2), 4.20 (q, 2H, CH2CH3), 4.33 (s, 2H, CH2C=C), 5.96 and 6.30 (s, 2xlH, C=CH2) and 11.38 (s, b, 2H, OH).

C-NMR (75 MHz, acetone-d~, ppm): 14.2 (CH3l), 61.25 (CH2CH3t), 64.75 and 66.9 (d, CH2Pt), 71.35 (CH2C=Ct), 126.15 (C=CH2t), 137.6 (C=CH2(-)) and 165.75 (C=O).

P-NMR (121.5 MHz, acetone-d~, Ppm): 47Ø
Example 2 1st staqe: 2- r 4-dimethoxYPhosphoryl)-2-oxa-butyll-acrylic acid ethyl ester (3) 7.45 g (50 mmol) ~-chloromethylacrylic acid ethyl ester were added at room temperature with stirring to a solution of 7.7 g (50 mmol) hydroxyethylphosphonic acid dimethyl ester, 5.05 g (50 mmol) TEA and 0.01 g phenothiazine in 40 ml absolute THF. The 30 process was then continued analogously to Example 1 (lst stage).
The fractional distillation produced 2.1 g [b.p. 115-120~C (0.005 mbar)] of a colourless liquid (16 % yield).

CA 022~0333 1998-10-1 Elemental analysis:

CloHl9O6p Calc.: C 45.11 H 7.19 (266.23) Found: C 45.45 H 7.26 IR (KBr, cm ): 645 (w), 732 (m), 820 (s), 954 (m), 1032 (s,b), 1105 (s), 1179 (s), 1267 (s), 1306 (s), 1375 (m,sh), 1464 (m,sh), 1640 (m), 1715 (s), 2234 (w), 2956 (m,sh) and 3472 (w,b).

10 H-NMR (300 MHz, CDCl~, ppm): 1.31 (t, 3H, CH3CH2), 2.10-2.21 (m, 2H, CH2P), 3.71-3.83 (m, 8H, 2xCH30 + CH7CH70), 4.18-4.28 (m, 4H, CHlCH70 + CH2C=), 5.89 and 6.29 (s, 2xlH, C=CH2).

C-NMR (75 MHz, CDCll, ppm): 14.2 (CH3CH21), 24.0 and 27.0 15 (CH2Pt), 52.3 (CH30), 60.95 (CH3CH2t), 64.6 (CH7CH70t), 69.0 (OCH2C=Ct), 126.0 (C=CH7t), 137.4 (C=5~(-)) and 165.6 (C=O(-)).

P-NMR (121.5 MHz, CDCl~, pPm): 62Ø
~0 2nd staqe: 2-r4-dihydroxyphosphorYl)-2-oxa-butyll-acrylic acid ethyl ester (4) r~~ ~~--/\P (OH)2 O ~ O (4) Analogously to Example 1 (2nd stage), 7.7 g (50 mmol) trimethylsilyl bromide were added dropwise to a solution of 6.1 g (23 mmol) of compound (3) and 0.01 g MEHQ in 20 ml absolute 30 methylene chloride. The mixture was stirred for a further 90 minutes under reflux, then concentrated, and the residue was reacted with 30 ml methanol and treated in accordance with Example 1 (2nd stage). After drying under a medium vacuum until the weight was constant, 4.3 g (79 % yield) of a viscous oil was 35 obtained as product.

CA 022~0333 1998-10-1 Elemental analysis:

C8Hl5O6P Calc.: C 40.34 H 6.35 (238.18) Found: C 40.86 H 6.52 IR (KBr, cm ): 718 (w), 820 (w), 1024 (s,sh), 1103 (s), 1178 (s,sh), 1273 (m,sh), 1307 (m), 1376 (m,sh), 1466 (w,sh), 1637 (m), 1717 (s), 2323 (b) and 2800-3300 (m,b).

10 H-NMR (300 MHz, acetone-d~, PPm): 1.28 (t, 3H, CH3), 2.07-2.24 (m, 2H, CHzP), 3.72-3.84 (m, 2H, CH7CH70), 4.15-4.25 (m, 4H, CH~CH~O + CHzC=C), 5.93 and 6.25 (s, 2xlH, CH2=) and 9.80 (s, 2H, OH).

C-NMR (75 MHz, acetone-d~, PPm): 13.0 (CH3), 27.8 and 30.3 (d, CH2P), 61.4 (CH7CH3), 65.58 (CH7CH70), 71.6 (CHzC=CHz), 125.7 (CH2C=CH2), 138.5 (CHzC=CH2) and 166.1 (C=O).

P-NMR (121.5 MHz, CDCl~, ppm): 60Ø
Example 3 1st staqe: 1,4-bis r l-(diethoxyphosphoryl)-l-hydroxymethyll-benzene (5) 1.1 g (0.01 mol) DABCO were added at ca. 15 C with stirring to a solution of 13.4 g (0.1 mol) terephthalic aldehyde and 29.0 g (0.2 mol) diethyl phosphite in 50 ml absolute acetonitrile.
After further stirring over night, the formed precipitate was 30 removed by suction, washed in each case with some acetonitrile and petroleum ether and dried until the weight was constant.
30.7 g (75 % yield) of a white solid (m.p.: 195-200~C) were obtained.

CA 022~0333 1998-10-1 Elemental analysis:

Cl6H28O8p2 Calc.: C 46.83 H 6.68 (410.34) Found: C 46.79 H 6.43 IR (KBr, cm ): 445 (w), 494 (w), 575 (s), 658 (w), 758 (m), 791 (w), 831 (w), 861 (w), 975 (s), 1022 (s), 1056 (s), 1205 (s), 1230 (s), 1392 (m), 1445 (w), 1478 (w), 1509 (w), 1702 (w), 2911 (w), 2988 (m) and 3263 (s,b).
H-NMR (300 MHz, DMSO-d~, ppm): 1.12-1.18 (m, 12H, CH3), 3.82-3.98 (m, 8H, CH2), 4.92 (d, 2H, CH-P), 6.20 (s, 2H, OH, H/D
exchange) and 7.38 (s, 4H, CH-arom.).

15 l3C NMR (100 MHz, DMSO-d~, Ppm): 16.13 and 16.23 (s, CH3), 61.68 and 62.08 (s, CH2), 68.31 and 69.93 (d, CH-P), 126.68 (s, CH-arom.) and 137.54 (s, quart. arom. C).

P-NMR (162 MHz, DMSO-d~, ppm): 21.9.
2nd staqe: 1,4-bisrl-~diethoxyPhosphoryl)-l-r(2-methylen-3-yl-ProPanoic acid ethYl ester)-oxylmethyll-benzene t6) 25 8.9 g (60 mmol) a-chloromethylacrylic acid ethyl ester were added at room temperature and with stirring to a solution of 12.3 g (0.03 mol) of compound (5), 6.05 g (60 mmol) TEA and 0.02 g phenothiazine in 100 ml absolute THF. After 30 minutes' stirring at room temperature, the mixture was heated under reflux for 16 30 hours. After cooling to room temperature, the formed precipitate was filtered off, washed once witk diethyl ether and twice with water. After drying of the residue at 60~C under a medium vacuum, 9.7 g (51 % yield) of a colourless resin were obtained.

CA 022~0333 1998-10-1 Elemental analysis:

C2sH44~l2P2 Calc-: C 52.98 H 6.99 (634.60) Found: C 52.98 H 7.08 IR (KBr, cm ): 580 (s), 751 (m), 795 (m), 859 (w), 967 (s), 1028 (s), 1055 ts), 1095 (s), 1177 (s), 1257 (s), 1308 (s,sh), 1391 (s,sh), 1445 (m,sh), 1508 (w), 1636 (m), 1716 (s), 2930 (m,sh) and 2982 (s).
lN-NMR (400 MHz, acetone-d~, ppm~: 1.10-1.22 (m, 18H, CH3), 3.95-4.01 (m, 8H, POCH2CH3), 4.10-4.16 (m, 8H, COCH2), 4.95 (d, 2H, CH), 5.97 and 6.27 (s, 2x2H, CH2=) and 7.43 (s, 4H, CH-arom.).

15 13C NMR (100 MHz, acetone-d,~, ppm): 14.16 (CH3-methacrylate), 16.37 (CH3-phosphonate) 60.73 (OCH2CH3-methacrylate), 62.9 and 63.2 (d, OCH2CH3-phosphonate), 68.70 and 68.83 (d, CH-P), 126.82 and 128.54 (CH2= and CH-arom.), 134.97 and 136.75 (CH2=C and C-arom.) and 165.37 (C=O).
P-NMR (121.5 MHz, DMSO-d~, PPm): 18.6.

3rd staqe: 1,4-bis r 1- ( dihydroxyphosphoryl)-1- r ( 2-methYlen-3-yl-ProPanoic acid ethyl ester)oxYlmethvll-benzene (7) (HO~P--CH~CH--P(OH)2 CH2 CH2=
C=O O=C
OC2H; OC~Hs 8.6 g (56 mmol) trimethylsilyl bromide were added dropwise to a 35 solution of 7.8 g (12.3 mmol) of compound (6) and 0.01 g MEHQ in 20 ml absolute methylene chloride, and the mixture obtained was CA 022~0333 1998-10-1 stirred under reflux for 75 minutes. The mixture was then concentrated in a rotary evaporator. After 20 ml methanol had been added to the residue, it was stirred over night and concentrated again in vacuo. The formed light-yellow powder was 5 taken up in 100 ml of a saturated NaHCO3 solution and washed twice with in each case 50 ml methylene chloride. The solution was then stirred up with activated charcoal and filtered. The filtrate was set to pH = 1 with concentrated hydrochloric acid, treated with 2 g NaCl and 50 ml water and then shaken out three 10 times with in each case 150 ml methylene chloride. The combined extracts were dried over Na2SO4 and concentrated until dry in a rotary evaporator. The residue was dried under a medium vacuum until the weight was constant. 4.3 g (66 96 yield) of a weakly yellowish crystalline product remained.
Elemental analysis:

C20H28O~2p2 Calc.: C 45.99 H 5.45 (522.39) Found: C 44.96 H 4.93 IR (KBr, cm ):412 (m), 569 (s), 646 (w), 815 (m), 941 (s), 1035 (s), 1093(s), 1176 (s), 1285 (sh), 1320 (sh), 1390 (sh), 1406 (m), 1460 (w), 1509 (w), 1636 (m), 1717 (s), 2987 (s) and 3440 (s,b)-H-NMR (300 MHz, DMSO-d~/CDCl~, ppm): 1.17 (t, 6H, CH3), 4.12-4.33 (m, 8H, CH2), 4.50-4.55 (d, 2H, CH), 6.08 and 6.27 (s, 2xlH, =CH2), 7.36 (s, 4H, CH-arom.) and 9-10 (4H, b, OH).

C-NMR ~100 MHz, DMSO-d~/CDCl~, ppm): 14.01 (CH3), 60.37 (OCH2CH3), 68.10 and 68.23 (d, CH-P), 125.87 and 127.49 (CH2= and CH-arom.), 135.64 and 136.85 (CH2--C and C-arom.) and 165.34 (C=O) .

35 lP-NMR (121.5 MHz, DMSO-d~, ppm): 15.1.

.._ CA 022~0333 1998-10-1 Example 4 1st staqe: r (dimethoxYPhosPhorYl ) -r ( 2-methylen-3-yl-propanoic acid ethyl ester)oxyl-methyllbenzene (8!

14.9 g (0.1 mol) ~-chloromethylacrylic acid ethyl ester were added at room temperature with stirring to a solution of 21.6 g (0.1 mol) [(dimethoxyphosphoryl)-1-hydroxymethyl]benzene, which 10 can be obtained by reacting dimethyl phosphite with benzaldehyde (F. Texier-Boullet, A. Foucaud, Synthesis 1982, 916), 10.1 g (0.1 mol) TEA and 0.02 g phenothiazine in 200 ml absolute THF. After 30 minutes' stirring at room temperature, the mixture was heated for 16 hours under reflux. After cooling to room temperature, 15 the formed precipitate was filtered off, and this was washed once with diethyl ether. The washing ether and the filtrate were diluted with 400 ml water, and the mixture obtained was extracted three times with in each case 100 ml ether. The combined organic extracts were washed with 100 ml saturated NaCl solution, dried 20 over Na2SO4 and concentrated in a rotary evaporator. The remaining oily residue was then destilled under a high vacuum.
15.9 g (49 % yield) of a colourless liquid [b.p.: 153-155~C (10-5 mbar)] were obtained.

25 Elemental analysis:

Cl5H2lO6P Calc.: C 54.88 H 6.45 (328.30) Found: C 54.10 H 6.24 30 IR (KBr, cm ): 465 (s,b), 701 (m), 771 (w), 832 (m), 1031 (s,sh), 1095 (s), 1181 (s), 1262 (s), 1309 (m), 1401 (w), 1453 (m), 1637 (w), 1718 (s), 2854 (w) and 2956 (m).

N-NMR (300 MHz, CDCl~, ppm): 1.29 (t, 3H, CH3CH2), 3.65-3.73 35 (dd, 6H, POCH3), 4.14-4.33 (m, 4H, CHz), 4.78 (d, lH, CH), 5.97 and 6.34 (s, 2xlH, CH2=) and 7.34-7.47 (m, 5H, CH-arom.).

CA 022~0333 1998-10-1 C-NMR (100 MHz, CDCl~, ppm): 14.45 (s, CH3-methacrylatet); 54.17 (d, CH3-OPt); 61.07 (OCH2CH3-methacrylatel); 69.88 (s, OCH2C=CH21);
77.34 and 79.31 (d, CH-Pt); 126.87 (s, CH2=l); 128.32 and 128.86 (s, CH-arom.t); 134.97 and 136.75 (CH2=C and C-arom.(-)); 165.37 5 (C=O(-)) P-NMR (121.5 MHz, CDCl~, ppm): 21.3 (s).

2nd staqe: 1-(dihYdroxYPhosPhoryl)-l- r ( 2-methylen-3-yl-propionic acid ethyl ester)-oxylmethyll-benzene (9!

~ ~, CH (9) =<
C=O
~C2Ha 20 17.2 g (0.1 mol) trimethylsilyl bromide were added dropwise to a solution of 14.4 g (44 mmol) of compound (8) and 0.01 g MEHQ
in 40 ml absolute methylene chloride, and the mixture obtained was stirred under reflux for 75 minutes. The mixture was then concentrated in a rotary evaporator, and the residue was reacted 25 with 40 ml methanol. The mixture was stirred for 4 hours and concentrated in vacuo. The formed resin was taken up in 200 ml of a saturated NaHCO3 solution and washed twice with 100 ml methylene chloride. The solution was stirred up with activated charcoal and filtered. The filtrate was then set to pH = 1 with 30 concentrated hydrochloric acid, treated with 4 g NaCl and 50 ml water and then shaken out three times with in each case 100 ml methylene chloride. The combined extracts were dried over Na2SO4 and concentrated until dry in a rotary evaporator. The residue was dried under a medium vacuum until the weight was constant.
35 10.0 g (76 % yield) of a sticky crystalline product were obtained.

CA 022~0333 1998-10-1~
.

Elemental analysis:

Cl3Hl706P Calc.: C 52.00 H 5.71 (300.25) Found: C 50.47 H 5.58 IR (KBr, cm ): 698 (s), 739 (w), 805 (w), 819 (w), 970 (s), 1026 (s,sh), 1094 (s,sh), 1178 (s,sh), 1280 (s,sh), 1320 (m), 1340 (m), 1402 (m,sh), 1453 (m,sh), 1490 (m), 1643 (m), 1713 (s), 2321 (m), 2910 (m), 2949 (m) and 2982 (m).
H-NMR (300 MHz, CDCl~, ppm): 1.22 (t, 3H, CH3), 4.06-4.17 (m, 4H, CH2), 4.50 (d, 2H, CH-P), 5.89 and 6.19 (s, 2xlH, CH2=), 7.18-7.33 (m, 5H, CH-arom.) and 10.79 (s, 2H, OH, H/D exch.).

C-NMR ~100 MHz, CDCl1, ppm): 14.08 (CH3); 60.86 (OCH2CH3); 68.49 (CH2OCH); 77.20 and 78.86 (d, CH-P); 127.49-128.25, 135.21, 136.15 (all C-arom. + CH2=C) and 166.08 (C=O).

P-NMR (121.5 MHz, CDCll, ppm): 20.1.
Example 5 Radical homopolYmerization of acrYlphosphonic acid (7) 25 2.61 g (5.0 mmol) of the acrylphosphonic acid (7) used as monomer and 2.5 mol% azobis(isobutyronitrile), relative to the monomer, were dissolved in 9.0 ml ethanol in a Schlenk vessel. The monomer solution was degassed by being repeatedly frozen under argon and defrosted under a medium vacuum and then polymerized 30 at 65~C under argon. On account of the difunctional monomer structure, crosslinked and therefore insoluble polymeric acrylphosphonic acid (7) was already deposited after 2 minutes.
The monomer conversion was 47.7 % after 1 hour. The formed polymer was insoluble.

CA 022~0333 1998-10-1 Example 6 ~mi n~tion of the hydrolYtic stabilitY of the monomeric acrylphosphonic acids 20 wt.% solutions in EtOD/H2O (1 : 1 parts by volume) were prepared from each of the monomeric acrylphosphonic acids (2) and (7) according to the invention and from monomeric 2-(methacryloyloxy)ethylphosphonic acid (10) as a comparative 10 example and were stored at 25 and 37 C. To determine the hydrolytic stability, an H-NMR spectrum was recorded after various times and was analysed for the formation of possible cleavage products.

15 It was shown that no hydrolytic cleavage of the polymerizable group had taken place in the case of the acrylphosphonic acids (2) and (7) according to the invention even after 3 months, whereas in the case of the conventional acrylphosphonic acid (10) the cleavage of the ethylphosphonic acid group began after just 20 a few hours at 25 C and was detectable by the presence of 2-hydroxyethylphosphonic acid as a cleavage product. This suggests a hydrolytic cleavage according to the following formula.

O O
25~ O,~_,P OH Monomer(lo) ~ OH (Comparative Example) Hydrolytic cleavage Example 7 ~mi n~tion of the adhesion to metal of the acrylphosphonic acids Wiron 88 (Thyssen-Bego), an Ni-Cr-Mo dental alloy customary in 35 the trade, was sandblasted and cleaned with superheated steam.
A primer consisting of 10.0 wt.% of the acrylphosphonic acid (7), .

CA 022~0333 1998-10-1~

45.0 wt.% water, 44.7 wt.% ethanol and 0.3 wt.% camphor quinone was then brushed on in a thin layer, and Variolink (Vivadent Ets., Liechtenstein), a commercial light-curing adhesive for filling composites, was applied to it and exposed to light. A
5 dividible Teflon mould (d=4mm, h=6mm) was then fixed with a securing means to the metal surface, and a light-curing filling composite, namely Tetric (Vivadent Ets., Liechtenstein) was polymerized in layers onto the metal surface in a volume predetermined by the Teflon mould and on an adhesion surface 10 thereby determined. The shear strength values were determined after 24 hours' storage in water at 3i C according to ISO-TR 11 405. The adhesive strength ascertained in the shear test gave an excellent value of 11.6 + 2.0 MPa.

Claims (28)

1. Hydrolysis-stable and polymerizable acrylphosphonic acids of the general formula (I), stereoisomers thereof and mixtures of these where R1, R2, R3, X, Y and n, unless stated otherwise, independently of one another have the following meanings:

R1 = hydrogen, C1 to C10 alkyl or C6 to C10 aryl, R2 = hydrogen, fluorine, C1 to C5 alkyl or phenyl, R3 = C1 to C8 alkylene, phenylene or is absent, Y = oxygen, sulphur, C1 to C8 alkylene or is absent, n = 1 or 2, and with the proviso that (a) for n = 1 X = hydrogen, fluorine, C1 to C5 alkyl or C6 to C12 aryl, and (b) for n = 2 X = C1 to C10 alkylene, C6 to C10 arylene, C7 to C20 arylenalkylene or is absent, and in which the individual alkyl, aryl, alkylene, arylene, phenyl, phenylene and arylenalkylene radicals can bear one or more substituents.
2. Acrylphosphonic acids according to Claim 1, wherein the variables of the formula (I), unless otherwise stated, independently of one another have the following meanings:

R1 = hydrogen, C1 to C5 alkyl or phenyl, R2 = hydrogen, fluorine or C1 to C3 alkyl, R3 = C1 to C3 alkylene, phenylene or is absent, Y = oxygen, C1 to C3 alkylene or is absent, n = 1 or 2, and with the proviso that (a) for n = 1 X = hydrogen, fluorine, C1 to C3 alkyl or phenyl, and (b) for n = 2 X = C1 to C6 alkylene, phenylene or is absent.
3. Process for the preparation of acrylphosphinic acids according to Claim 1 or 2, wherein .alpha.-halomethylacrylic acid esters of the general formula (II) are reacted with protected mono- or difunctional phosphonic acid esters of the general formula (III) and the protective groups are cleaved off, with U = halogen, SG = protective group and the remaining variables being as defined in Claim 1.
4. Use of the acrylphospyhonic acids according to Claim 1 or 2 as a component of an adhesive, of a polymer, of a composite, of a cement, of a shaped body and in particular of a dental material.
5. Use according to Claim 4, wherein the dental material is a dental adhesive, a fixing cement or a filling composite.
6. Use according to Claim 4 or 5, wherein the acrylphosphonic acids are present in at least partially polymerized form.
7. Dental material, which contains acrylphosphonic acid according to Claim 1.
8. Dental material, which contains acrylphosphonic acid according to Claim 2.
9. Dental material according to Claim 7 or Claim 8, which contains the acrylphosphonic acid in at least partially polymerized form.
10. A polymer obtained by polymerizing at least one acrylphosphonic acid according to Claim 1 or Claim 2.
11. A copolymer obtained by copolymerizing an acrylphosphonic acid according to Claim 1, with a radically polymerizable comonomer.
12. A copolymer obtained by copolymerizing an acrylphosphonic acid according to Claim 2, with a radically polymerizable comonomer.
13. A copolymer according to Claim 11 or Claim 12 wherein the comonomer is a difunctional cross linking monomer.
14. A copolymer according to Claim 11 or Claim 12 wherein the comonomer is selected from the group consisting of bisphenol-A-di(meth)acrylate, an addition product of methacrylic acid and bisphenol-A-diglycidyl ether, an addition product of hydroxy ethyl methacrylate and 2,2,4-trimethyl-hexamethylene diisocynate, di ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetra ethylene glycol di(meth) acrylate, decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerithritol tetra(meth)acrylate, butanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate and 1,12-do decanediol di(meth)acrylate.
15. A method for polymerizing acrylphosphonic acids according to Claim 1, wherein the acrylphosphonic acid is polymerized in the presence of an initiator and optionally a radically polymerizable comonomer.
16. A method for polymerizing acrylphosphonic acids according to Claim 2, wherein the acrylphosphonic acid is polymerized in the presence of an initiator and optionally a radically polymerizable comonomer.
17. A method according to Claim 15 or Claim 16 wherein the initiator is a radical initiator or a photo initiator.
18. A material selected from the group consisting of an adhesive, a polymer, a cement and a shaped body, which material contains at least one acrylphosphonic acid according to Claim 1 or Claim 2.
19. A dental material which comprises:
(a) from 1 to 99 wt.% of at least one acrylphosphonic acid according to Claim 1;
(b) from 0.01 to 5 wt.% of a radical initiator;
(c) optionally, up to 80 wt.% of at least one radically polymerizable comonomer;
(d) optionally, up to 95 wt.% of a solvent; and (e) optionally, up to 90 wt.% of a filler.
20. A dental material which comprises:
(f) from 1 to 99 wt.% of at least one acrylphosphonic acid according to Claim 2;
(g) from 0.01 to 5 wt.% of a radical initiator;
(h) optionally, up to 80 wt.% of at least one radically polymerizable comonomer;
(i) optionally, up to 95 wt.% of a solvent; and (j) optionally, up to 90 wt.% of a filler.
21. A dental material according to Claim 19 or Claim 20 wherein the acrylphosphonic acid is present in an amount from 20 to 70 wt.%.
22. A dental material according to Claim 19 or Claim 20 wherein the radical initiator is present in the amount from 0.1 to 2.0 wt.%.
23. A dental material according to Claim 19 or Claim 20 wherein the radically polymerizable comonomers are present in an amount up to 60 wt.%.
24. A dental material according to Claim 19 or Claim 20 wherein the filler is present in an amount up to 20 wt.%.
25. A dental material according to Claim 19 or Claim 20 wherein the filler is present in an amount from 20 to 60 wt.%.
26. A dental material according to Claim 19 or Claim 20 wherein the filler is present in an amount from 60 to 85 wt.%.
27. An adhesive dental material according to Claim 19 or Claim 20 wherein the acrylphosphonic acid is present in an amount of 20 to 70 wt.%, the filler is present in an amount of up to 20 wt.%.
28. A cement dental material according to Claim 19 or 20 wherein the acrylphosphonic acid is present in an amount of 20 to 70 wt.% and the filler is present in an amount of from 20 to 60 wt.%.
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