Polymerisable materials which are based on hardenable...

Details Polymerisable materials which are based on hardenable... Polymerisable materials which are based on hardenable...

2001-09-19

2003-05-20

Seidleck, James J. (Department: 1711)

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

Synthetic resins

Compositions to be polymerized by wave energy wherein said...

C522S148000, C522S172000, C522S099000, C523S109000, C523S115000, C523S116000, C523S118000, C523S120000, C433S180000, C433S226000, C433S228100, C424S401000, C528S032000, C548S406000

Reexamination Certificate

active

06566413

ABSTRACT:

The present invention relates to polymerizable compositions, based on curable siloxane compounds, for dental and dental engineering applications.
Hitherto predominantly ethylenically unsaturated monomers, preferably methacrylate and acrylate monomers, have been used in polymerizable dental compositions.
The 2,2-bis[4,1-phenyleneoxy(2-hydroxy-3,1-propanediyl)-methacrylic acid ester]-propylidene (bis-GMA) described by Bowen [U.S. Pat. No. 3,066,112] is used particularly frequently. Mixtures of this methacrylate with triethylene glycol dimethacrylate (TEGDMA) still serve even today as the standard formulation for dental plastic direct filling materials. Methacryl derivatives of the double-formylated bis-(hydroxymethyl)tricyclo[5.2.1.0
2,6
]decane have also proved themselves as monomers for dental composites [W. Gruber at al., DE-A-27 14 538; W. Schmitt et al., DE-C-28 16 823; J. Reiners et al., EP-A-0 261 520].
Common to all these compositions is the disadvantageous polymerization shrinkage occurring during polymerization. This can lead for example in the application as filling material to the formation of discolorations at the cavity edge of the tooth or even to the development of edge cracks with subsequent risk of secondary caries.
Attempts have therefore been made in the past to reduce the polymerization shrinkage of the dental compositions through as great as possible a proportion of inorganic fillers. However, this normally leads to a clear increase in the viscosity of such compositions with handling drawbacks for the user, who must then have recourse where necessary to auxiliary means such as e.g. ultrasound for the processing of these materials [EP-0-480 472].
Customarily used dental monomers in most cases contain one or at most two polymerizable groups. A higher functionality for radically crosslinking groups per molecule leads as a rule to very highly viscous substances which can be mixed with filler only with difficulty and lead to very brittle materials in the cured state.
However, low-functionalized monomers have the disadvantage that they provide few linkage points for crosslinking and are therefore still present as monomers even after the curing reaction if the polymerization of all the monomers is not complete (which is practically never 100% achieved). These so-called residual monomers can be dissolved out of the dental material over an extended period of time and lead to unwanted side-effects in the organism.
The object of the present invention was therefore to provide monomers for dental compositions which, despite a high density of groups capable of polymerization, display a low viscosity, permit a high filler uptake and lead to compositions with a low polymerization shrinkage.
The object was achieved by the provision of novel monomers of the following general formula (I):
in which:
n=0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 preferably 1, 2, 3, 4, 5;
A=H or C
1
-C
15
alk(en)yl, preferably methyl, ethyl, propyl, butyl, vinyl, ethinyl, allyl, C
3
-C
15
cycloalk(en)yl, preferably cyclopentyl, cyclohexyl, cyclopentadienyl, cyclohexenyl, C
6
-C
12
aryl, preferably phenyl, tolyl, xylyl, C
8
-C
18
alkaryl, preferably phenylethylenyl, where, in the said radicals, in each case one or more C atoms can be replaced by O, C═O, O(C═O), SiR
2
and/or NR, R being an aliphatic radical with 1 to 7 C atoms, in which one or more C atoms can be replaced by O, C═O, and/or O(C═O);
B=E or a linear, branched or polycyclic aliphatic- or aromatic-groups-containing hydrocarbon radical which links 2 to 10, preferably 2 to 5 cyclosiloxane radicals defined above, less B, to one another and contains 2 to 50, preferably 2 to 30 C atoms and additionally 0 to 30, preferably 0 to 20 other atoms from the group O, N, S, P, Si, Cl, F, Br, I and from which correspondingly 1 to 9, preferably 1 to 4 of the above defined cyclosiloxane radicals, less B, are pending; particularly preferred radicals B are: di(prop-3-yl)ether, di(prop-3-yl)sulfide, di(prop-3-yl)amine, di(prop-3-yl)-methyl-amine, tri(prop-3-yl)amine, di(prop-3-yl)urea, di(prop-3-yl)carbonate, ethylene glycol di(prop-3-yl)carbonate, diethylene glycol di(prop-3-yl)carbonate, ethylene glycol di(prop-3-yl)ether, diethylene glycol di(prop-3-yl)ether, 1,2-propanediol di(prop-3-yl)ether, 1,3-propanediol di(prop-3-yl)ether, 1,3-butanediol di(prop-3-yl)ether, 1,4-butanediol di(prop-3-yl)ether, 1,4-butenediol di(prop-3-yl)ether, 1,4-butinediol di(prop-3-yl)ether, 1,5-pentanediol di(prop-3-yl)ether, 16-hexanediol di(prop-3-yl)ether, 1,8-octanediol di(prop-3-yl)ether, 1,9-nonanediol di(prop-3-yl)ether, 1,10-decanediol di(prop-3-yl)ether, 1,12-dodecanediol di(prop-3-yl)ether, oxalic acid di(prop-3-yl)ester, malonic acid-di(prop-3-yl)ester, succinic acid di(prop-3-yl)ester, adipic acid di(prop-3-yl)ester, sebacic acid di(prop-3-yl)ester, 1,2-ethanediyl, 1,4-pentadienyl, 1,5-pentanediyl, 1,5-hexadienyl, 1,6-heptadienyl, 1,7-octadienyl, 1,8-nonadienyl, 1,9-decadienyl, 1,11-dodecadienyl, p-di(eth-2-yl)benzene, bis-4-(prop-3-yl)oxyphenyl)-sulfone, bis-4-(prop-3-yl)oxyphenyl)-ketone, bis-4-(prop-3-yl)-oxyphenyl)methane, 1,1-bis-(4-(prop-3-yl)oxyphenyl)-ethane, 2,2-bis-(4-(prop-3-yl)oxyphenyl)-propane, 2,2-bis-(4-(prop-3-yl)oxyphenyl)-perfluoropropane, 2,2-bis-(4-(prop-3-yl)oxy-3,5-dibromo-phenyl)-propane, 3,3-bis-(4-(prop-3-yl)-oxyphenylpentane, 4,4-bis-(4-(prop-3-yl)oxy-phenyl)-heptane, 1,1-bis-(4-(prop-3-yl)oxyphenyl)-cyclopentane, 1,1-bis-(4-(prop-3-yl)-oxyphenyl)-cyclohexane, 1,1-bis-(4-(prop-3-yl)oxyphenyl)-3,3,5-trimethylcyclohexane, 1,1,1-tris-(4-(prop-3-yl)oxyphenyl)-ethane, bis-((prop-3-yl-ether)oxy)-tricyclo[5.2.1.0
2,6
]decane:
E=A or a polymerizable group G—Q—L, where on average up to 50%, preferably 25% or less of the groups E correspond to representatives of A;
G=C
1-10
alk(en)ylene, preferably ethylene, methylethylene, propylene, butylene, hexylene, ethenylene, propenylene;
Q=O, N—A or a di- or polyvalent linear, branched or cyclic alcohol, amine or aminoalcohol radical with 2 to 10 C atoms, preferably ethanediol-diyl, glycerol-triyl, trimethylolpropane -triyl, pentaerythritol-tetryl;
L=an organic radical, containing a C═C double bond, with 2 to 10 C atoms, preferably acryl or methacryl.
Compounds according to formula (I) are cyclic siloxanes, in which one or more siloxane rings can occur per molecule. However, compounds in which annelated siloxane ring systems are present are expressly excluded.
The preparation of compounds of the general formula (I) takes place by suitable methods.
Si—H-functional cyclosiloxanes can be linked to C—C-unsaturated organic structures by hydrosilylation in particular (B. Marciniec: Comprehensive Handbook on Hydrosilylation, Pergamon Press, 1992). The properties of both monomers and polymers can be set in desired manner in this way.
For example, 1,3,5,7-tetramethylcyclotetrasiloxane can be linked to a representative of (I) in a solvent, such as toluene, under the influence of precious-metal catalysts, such as Speir catalysts or else Wilkinson catalysts, with four mol allyl methacrylate. Instead of the cyclotetrasiloxane, a commercially available SiH cycle mixture (a mixture of (SiMeHO)
n
with n preferably 4, 5, 6) can also be used. Instead of allyl methacrylate, other allyl ethers, esters or amides of (meth)acryl-functional organic molecules can be used.
In the case of the reaction of polyfunctional SiH-cyclosiloxanes with likewise multiple C—C unsaturated organic structures, all C—C unsaturated functions of the organic structure can be saturated with in each case a cyclosiloxane ring through a suitable reaction procedure. However, pre-crosslinked intermediate products can also be produced by a different choice of stoichiometry or reaction procedure.
Both possibilities are meant here.
These SiH-functional preliminary stages can for example be reacted with allyl methacrylate to produce further representatives of (I).
The particularly preferred structures shown in the following are as

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